Hydroprocessing for lubricant basestock production

ABSTRACT

Methods are provided for hydroprocessing a feed (such as hydrotreating, hydrocracking, or hydrofining a feed) to generate a product with a reduced or minimized aromatics content relative to the severity of the hydroprocessing conditions. In some types of hydroprocessing applications, it can be desirable to select the severity of hydroprocessing conditions to achieve a desired level of removal for sulfur, a desired level for removal of nitrogen, and/or a desired level for increasing the viscosity index of a feed. The severity for heteroatom removal and/or viscosity index uplift can also correspond to an amount of conversion of a feed to lower boiling point products, so the lowest severity conditions suitable for achieving a product quality can be desirable. By improving the aromatics saturation during hydroprocessing, the severity of subsequent aromatics saturation processes can be reduced.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/082,273 filed Nov. 20, 2014, U.S. Provisional Application Ser.No. 62/152,083 filed Apr. 24, 2015 and U.S. Provisional Application Ser.No. 62/152,092 filed Apr. 24, 2015, which are herein incorporated byreference in their entirety.

FIELD

Systems and methods are provided for production of lubricant oilbasestocks.

BACKGROUND

As the supply of low sulfur, low nitrogen crudes decrease, refineriesare processing crudes with greater sulfur and nitrogen contents at thesame time that environmental regulations are mandating lower levels ofthese heteroatoms in products. Consequently, a need exists forincreasingly efficient desulfurization and denitrogenation catalysts.

U.S. Pat. Nos. 8,722,563 and 8,722,564 describe multimetallichydroprocessing catalysts prepared by forming a catalyst precursor andthen heating the catalyst precursor to form the catalyst. Themultimetallic catalysts are described as having improved activity forhydrodenitrogenation of various types of feeds.

U.S. Pat. No. 6,620,313, U.S. Pat. No. 7,232,515, and U.S. Pat. No.7,513,989 describe various types of processing sequences that includehydroprocessing in the presence of a bulk multimetallic catalyst. Theprocesses are described as being suitable for production of lubricantbasestocks.

SUMMARY

In an aspect, a process for selectively hydroconverting a raffinateproduced from solvent refining a lubricating oil feedstock is provided,including conducting the lubricating oil feedstock to a solventextraction zone and separating therefrom an aromatics rich extract and aparaffins rich raffinate; stripping the raffinate of solvent to producea raffinate feed having a dewaxed oil viscosity index from about 80 toabout 105 and a final boiling point of no greater than about 650° C.;passing the raffinate feed to a first hydroconversion zone andprocessing the raffinate feed in the presence of a mixed metal catalystunder hydroconversion conditions; and passing the first hydroconvertedraffinate to a second reaction zone and conducting cold hydrofinishingof the first hydroconverted raffinate in the presence of ahydrofinishing catalyst under cold hydrofinishing conditions, whereinthe mixed metal catalyst comprises a sulfided mixed metal catalystformed by sulfiding a mixed metal catalyst precursor composition, themixed metal catalyst precursor composition being produced by a) heatinga composition comprising at least one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a reaction product formed from (i) afirst organic compound containing at least one amine group, and (ii) asecond organic compound separate from said first organic compound andcontaining at least one carboxylic acid group to a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first andsecond organic compounds to form a reaction product in situ thatcontains an amide moiety, unsaturated carbon atoms not present in thefirst or second organic compounds, or both; b) heating a compositioncomprising one metal from Group 6 of the Periodic Table of the Elements,at least one metal from Groups 8-10 of the Periodic Table of theElements, and a reaction product formed from (iii) a first organiccompound containing at least one amine group and at least 10 carbonatoms or (iv) a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, but not both (iii)and (iv), wherein the reaction product contains additional unsaturatedcarbon atoms, relative to (iii) the first organic compound or (iv) thesecond organic compound, wherein the metals of the catalyst precursorcomposition are arranged in a crystal lattice, and wherein the reactionproduct is not located within the crystal lattice, to a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first orsecond organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds; or c) heating a composition comprising at least onemetal from Group 6 of the Periodic Table of the Elements, at least onemetal from Groups 8-10 of the Periodic Table of the Elements, and apre-formed amide formed from (v) a first organic compound containing atleast one amine group, and (vi) a second organic compound separate fromsaid first organic compound and containing at least one carboxylic acidgroup, to form additional in situ unsaturated carbon atoms not presentin the first organic compound, the second organic compound, or both, butnot for so long that the pre-formed amide substantially decomposes,thereby forming a catalyst precursor containing in situ formedunsaturated carbon atoms.

In another aspect, a process for producing a lubricating oil feedstockis provided, including exposing a feedstock to a mixed metal catalystunder effective hydroprocessing conditions to form a hydroprocessedeffluent; separating the hydroprocessed effluent to form at least a gasphase effluent and a liquid hydroprocessed effluent; optionally exposingat least a portion of the liquid hydroprocessed effluent to ahydrocracking catalyst under effective hydrocracking conditions to forma hydrocracked effluent; exposing at least a portion of the optionallyhydrocracked effluent to a dewaxing catalyst under effective catalyticdewaxing conditions to form an optionally hydrocracked, dewaxedeffluent, wherein the mixed metal catalyst comprises a sulfided mixedmetal catalyst formed by sulfiding a mixed metal catalyst precursorcomposition, the mixed metal catalyst precursor composition beingproduced by a) heating a composition comprising at least one metal fromGroup 6 of the Periodic Table of the Elements, at least one metal fromGroups 8-10 of the Periodic Table of the Elements, and a reactionproduct formed from (i) a first organic compound containing at least oneamine group, and (ii) a second organic compound separate from said firstorganic compound and containing at least one carboxylic acid group to atemperature from about 195° C. to about 250° C. for a time sufficientfor the first and second organic compounds to form a reaction product insitu that contains an amide moiety, unsaturated carbon atoms not presentin the first or second organic compounds, or both; b) heating acomposition comprising one metal from Group 6 of the Periodic Table ofthe Elements, at least one metal from Groups 8-10 of the Periodic Tableof the Elements, and a reaction product formed from (iii) a firstorganic compound containing at least one amine group and at least 10carbon atoms or (iv) a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, but not both (iii)and (iv), wherein the reaction product contains additional unsaturatedcarbon atoms, relative to (iii) the first organic compound or (iv) thesecond organic compound, wherein the metals of the catalyst precursorcomposition are arranged in a crystal lattice, and wherein the reactionproduct is not located within the crystal lattice, to a temperature fromabout 195° C. to about 250° C. for a time sufficient for the first orsecond organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds; or c) heating a composition comprising at least onemetal from Group 6 of the Periodic Table of the Elements, at least onemetal from Groups 8-10 of the Periodic Table of the Elements, and apre-formed amide formed from (v) a first organic compound containing atleast one amine group, and (vi) a second organic compound separate fromsaid first organic compound and containing at least one carboxylic acidgroup, to form additional in situ unsaturated carbon atoms not presentin the first organic compound, the second organic compound, or both, butnot for so long that the pre-formed amide substantially decomposes,thereby forming a catalyst precursor containing in situ formedunsaturated carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically shows an example of a configuration suitable forprocessing a feed to produce lubricant basestock products.

FIG. 2 shows processing conditions and results for hydrodenitrogenationof a feed in the presence of various catalysts.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Overview

In various aspects, methods are provided for hydroprocessing a feed(such as hydrotreating, hydrocracking, or hydrofining a feed) togenerate a product with a reduced or minimized aromatics contentrelative to the severity of the hydroprocessing conditions. In sometypes of hydroprocessing applications, it can be desirable to select theseverity of hydroprocessing conditions to achieve a desired level ofremoval for sulfur, a desired level for removal of nitrogen, and/or adesired level for increasing the viscosity index of a feed. The severityfor heteroatom removal and/or viscosity index uplift can also correspondto an amount of conversion of a feed to lower boiling point products, sothe lowest severity conditions suitable for achieving a product qualitycan be desirable. Some aromatics saturation is performed during thishydroprocessing, but typically one or more additional aromaticssaturation steps are required in order to achieve a target level ofaromatics in a resulting product. By improving the aromatics saturationduring hydroprocessing, the severity of subsequent aromatics saturationprocesses can be reduced.

In some aspects, the methods can include use of a catalyst formed from acatalyst precursor composition comprising at least one metal from Group6 of the Periodic Table of the Elements, at least one metal from Groups8-10 of the Periodic Table of the Elements, and a reaction productformed from (i) a first organic compound containing at least one aminegroup and at least 10 carbons or (ii) a second organic compoundcontaining at least one carboxylic acid group and at least 10 carbons,but not both (i) and (ii).

In other aspects, the process can use a catalyst formed from a catalystprecursor composition comprising at least one metal from Group 6 of thePeriodic Table of the Elements, at least one metal from Groups 8-10 ofthe Periodic Table of the Elements, and a reaction product formed from(i) a first organic compound containing at least one amine group, and(ii) a second organic compound separate from said first organic compoundand containing at least one carboxylic acid group. More broadly, thisaspect of the present disclosure relates to use of a catalyst formedfrom a catalyst precursor composition comprising at least one metal fromGroup 6 of the Periodic Table of the Elements, at least one metal fromGroups 8-10 of the Periodic Table of the Elements, and a condensationreaction product formed from (i) a first organic compound containing atleast one first functional group, and (ii) a second organic compoundseparate from said first organic compound and containing at least onesecond functional group, wherein said first functional group and saidsecond functional group are capable of undergoing a condensationreaction and/or a (decomposition) reaction causing an additionalunsaturation to form an associated product.

In still other aspects, the process can use a catalyst formed from acatalyst precursor composition comprising at least one metal from Group6 of the Periodic Table of the Elements, at least one metal from Groups8-10 of the Periodic Table of the Elements, and a reaction productcomprising an amide group. In this type of aspect, the reaction productis formed prior to incorporation into the catalyst precursor. Thereaction product is an amide-containing reaction product formed from anex-situ reaction of (i) a first organic compound containing at least oneamine group, and (ii) a second organic compound separate from said firstorganic compound and containing at least one carboxylic acid group.

Use of a Mixed Metal Catalyst Formed from a Suitable Precursor as aHydrotreating Catalyst for Lubricant Basestock Production

In various aspects, methods are provided for improving the yield ofdistillate products from hydroprocessing (including hydrotreatment,hydrocracking, and/or catalytic dewaxing) of gas oil feedstocks, such asvacuum gas oil feeds or other feeds having a similar type of boilingrange, during the production of lubricant base oils. In addition tousing a mixed metal catalyst formed from a suitable precursor, themethods can involve stripping of gases and/or fractionation to separateout a distillate fraction during initial hydrotreatment of a feed. Thiscan allow for an improved yield of distillate products at a desiredlevel of conversion, such as a level of conversion selected forprocessing a feedstock to generate lubricating oil basestocks. Theimproved yield of distillate can be achieved while reducing orminimizing production of lower boiling compounds, such as light ends ornaphtha boiling range products. Additionally or alternately, use of acatalyst derived from a suitable precursor composition whilehydroprocessing a gas oil feedstock can result in reduced or minimizedlevels of aromatics in the resulting lubricant basestocks at a desiredlevel of feed conversion.

As an example, some improvements in distillate product yield can beachieved based on separation or removal of contaminant gases duringhydrotreatment of a feedstock. This can reduce the required severity ofsubsequent processing stages, allowing for less conversion of desireddistillate boiling range products to naphtha or lower boiling rangeproducts. Removal of contaminant gases can also reduce the temperaturerequired to achieve a desired level of conversion to distillates, oralternatively, increase the amount of conversion at a specifiedtemperature. Other improvements in distillate yield can be achieved byfractionating the feedstock during hydrotreatment, so that distillateboiling range components are exposed to fewer hydroprocessing stages.Avoiding exposure of distillate boiling range products to additionalhydroprocessing, such as a second hydrotreatment stage, can preventfurther conversion of such products to naphtha or lower boiling rangeproducts. Still other improvements in distillate yield can be achievedby stripping contaminant gases and/or fractionating the hydrotreatedfeedstock after hydrotreatment and before hydrocracking. Once again,this can reduce additional conversion of products by avoiding exposureto a downstream hydrocracking stage or reducing the severity of such astage.

The yield improvements from performing a separation betweenhydrotreatment and hydrocracking can be further enhanced by using amixed metal catalyst formed from a suitable catalyst precursor as thehydrotreating catalyst. It has been discovered that a catalyst formedfrom a suitable catalyst precursor can provide an unexpectedly improvedactivity for aromatic saturation at a given level of process severityfor hydrodenitrogenation and/or hydrodesulfurization. Thus, use of acatalyst formed from a suitable catalyst precursor in an initialhydrotreatment stage can reduce or minimize the need to increase processseverity to achieve a target level of aromatics.

As an example, a typical reaction system for producing a lubricantbasestock can include a hydrotreating stage for removal of heteroatoms;a hydrocracking stage for increasing the viscosity index of theresulting lubricant basestock product; a dewaxing stage for improvingcold flow properties of the product(s), such as pour point; and anaromatic saturation stage for achieving a final aromatics target levelin the product(s). Using a catalyst formed from a suitable catalystprecursor can allow the hydrotreating stage to be operated at a severitysufficient for heteroatom removal in order to convert the initial feedinto a hydrotreated effluent with a reduced content of sulfur andnitrogen. The unexpected aromatics saturation benefit of the catalystformed from a suitable precursor can reduce or minimize the need toperform additional conversion of the feed in order to achieve a desiredlevel of aromatics saturation in the final product. In addition toimproving yield by avoiding excess conversion during hydrotreatment,additional yield improvement can be achieved by performing a separationon the hydrotreated effluent, such as to remove distillate and lowerboiling range components. This type of separation can remove distillatefuel components in the hydrotreated effluent before such components arecracked to less valuable naphtha or light ends boiling range compounds.This can also allow subsequent stages to operate under “sweet”conditions. Operating under sweet conditions can allow the subsequenthydrocracking and dewaxing reactions to have higher selectivity forimproving product properties at a given level of conversion.

FIG. 1 shows an example of a reaction system suitable for production oflubricant basestocks. It is noted that FIG. 1 includes a variety ofreaction system elements, but not all elements are required in eachpossible configuration. For example, in FIG. 1, reactors and/or stagesand/or catalyst beds 110, 120, and 130 are shown, but in various aspectseither one or two of reactors 110, 120, and/or 130 may be omitted.

In FIG. 1, reactors 110, 120, and/or 130 schematically representhydroprocessing of a feed prior to separation. The hydroprocessing inreactors 110, 120, and/or 130 can typically correspond tohydroprocessing of a feed in the presence of 500 wppm or more of sulfur.In the example shown in FIG. 1, a feed 105 is introduced into a firstreactor 110 containing a hydrotreating catalyst. The effluent fromreactor 110 is passed into reactor 120 containing a first hydrocrackingcatalyst. The effluent from reactor 120 is passed into reactor 130containing a second hydrotreating catalyst. The sequence of reactors110, 120, and 130 in FIG. 1 is provided for convenience of illustratingprocessing of a feed. It is understood that any convenient ordering ofreactors 110, 120, and 130 may be used and/or any one or any two ofreactors 110, 120, and 130 may be omitted. For example, other suitableconfigurations could include having a hydrocracking reactor or bed 120followed by a hydrotreating reactor or bed 110 without secondhydrocracking reactor 130; having only one or more hydrocrackingreactors 120 and/or 130; having only hydrotreating reactor 110; or anyother convenient combination.

The effluent from the final reactor or bed of reactors 110, 120, and 130can then be passed into a separation stage 140. In FIG. 1, separationstage 140 is schematically shown as a fractionation stage. Such afractionation stage can be suitable for separating the hydroprocessedeffluent from the hydroprocessing reactors or beds 110, 120 and/or 130into a plurality of fractions, such as light ends fraction, one or morenaphtha boiling range fractions, one or more distillate boiling rangefractions, optionally one or more lubricant boiling range fractions, anda bottoms fraction. Alternatively, separation stage 140 can correspondto a separate for separating light ends and contaminant gases generatedduring hydroprocessing (such as H₂S and NH₃) from the liquid productportions of the hydroprocessed effluent. More generally, any otherconvenient type of separation stage can be used as separation stage 140,including combinations of separators and fractionators.

Depending on the nature of the separation in separation stage 140, atleast a portion of the liquid hydroprocessed effluent is passed into ahydrocracking and/or aromatic saturation reactor 150. Due to the initialhydroprocessing reactor(s) and the separation stage 140, the sulfurcontent of the hydroprocessed effluent can generally be sufficiently low(such as 500 wppm or less) for operating aromatic saturation and/orhydrocracking reactor or bed(s) 150 under sweet processing conditions.In some optional aspects, the hydrocracking catalyst may be omitted. Insome optional aspects, the aromatic saturation catalyst may be omitted.In some optional aspects, the aromatic saturation and/or hydrocrackingreactor 150 may be omitted. The effluent from reactor 150 can then bepassed into a dewaxing reactor or bed 160 for catalytic dewaxing. Thedewaxed effluent can then optionally be passed into hydrofinishingreactor or bed 170. The effluent from dewaxing reactor 160 orhydrofinishing reactor 170 can correspond to the final effluent, whichcan then be fractionated to form one or more desired fuel and/orlubricant boiling range products.

Depending on the aspect, the initial reactors 110, 120, and/or 130 canbe used to desulfurize and denitrogenate a feedstock, saturate somearomatics, and/or potentially provide some increase in viscosity index.For example, the hydrocracking reactor 150 can increase the viscosityindex (VI) of a resulting lubricant base stock product. The dewaxingreactor 160 can reduce the pour point of a resulting lubricant basestock product. The aromatics saturation catalyst in reactor 150 and/orthe hydrofinishing catalyst in reactor 170 can further reduce thearomatics content of the resulting product.

In various aspects, a mixed metal catalyst formed from a suitableprecursor can be used in one or more reactors of the reaction systemschematically represented in FIG. 1. A mixed metal catalyst formed froma suitable precursor can be suitable for hydroprocessing under sourconditions, such as for hydrotreating in reactor 110, hydrocracking inreactor 120, hydrocracking in second hydrocracking reactor 130, or in acombination thereof. Additionally or alternately, a mixed metal catalystformed from a suitable precursor can be suitable for hydrocracking in ahydrocracking reactor 150, for aromatic saturation/hydrofinishing inreactors 150 and/or 170, or a combination thereof.

As one example of a suitable configuration, a feed can initially behydroprocessed under sour conditions, such as by exposing the feed toone or more beds of hydrotreatment catalyst under effectivehydrotreating conditions. The hydrotreated feed can optionally behydrocracked under effective (sour) hydrocracking conditions. Thehydroprocessed feed can then be fractionated to form at least a lightends fraction, a distillate fraction corresponding to a diesel fuelproduct, and a bottoms fraction for further processing. Optionally, aplurality of fuel products can be formed by fractionation, such as oneor more naphtha boiling range fractions and one or more distillateboiling range fractions. The bottoms fraction can then be hydrocrackedunder effective (sweet) hydrocracking conditions, followed by catalyticdewaxing under effective dewaxing conditions. Optionally, thehydrocracked, dewaxed effluent can then be hydrofinished prior tofractionation to form desired fuel and lubricant boiling range products.

In this discussion, the severity of hydroprocessing performed on a feedcan be characterized based on an amount of conversion of the feedstock.In various aspects, the reaction conditions in the reaction system canbe selected to generate a desired level of conversion of a feed.Conversion of a feed is defined in terms of conversion of molecules thatboil above a temperature threshold to molecules below that threshold.The conversion temperature can be any convenient temperature. Unlessotherwise specified, the conversion temperature in this discussion is aconversion temperature of 700° F. (371° C.).

The amount of conversion can correspond to the total conversion ofmolecules within any stage of the reaction system that is used tohydroprocess the lower boiling portion of the feed from the vacuumdistillation unit. The amount of conversion desired for a suitablefeedstock can depend on a variety of factors, such as the boiling rangeof the feedstock, the amount of heteroatom contaminants (such as sulfurand/or nitrogen) in the feedstock, and/or the nature of the desiredlubricant products. Suitable amounts of conversion across allhydroprocessing stages can correspond to at least about 25 wt %conversion of 700° F.+(371° C.+) portions of the feedstock to portionsboiling below 700° F., such as at least about 35 wt %, or at least about45 wt %, or at least about 50 wt %. In various aspects, the amount ofconversion is about 75 wt % or less, such as about 65 wt % or less, or55 wt % or less. It is noted that the amount of conversion refers toconversion during a single pass through a reaction system. For example,a portion of the unconverted feed (boiling at above 700° F.) can berecycled to the beginning of the reaction system and/or to anotherearlier point in the reaction system for further hydroprocessing.

In this discussion, a stage can correspond to a single reactor or aplurality of reactors. Optionally, multiple parallel reactors can beused to perform one or more of the processes, or multiple parallelreactors can be used for all processes in a stage. Each stage and/orreactor can include one or more catalyst beds containing hydroprocessingcatalyst. Note that a “bed” of catalyst in the discussion below canrefer to a partial physical catalyst bed. For example, a catalyst bedwithin a reactor could be filled partially with a hydrocracking catalystand partially with a dewaxing catalyst. For convenience in description,even though the two catalysts may be stacked together in a singlecatalyst bed, the hydrocracking catalyst and dewaxing catalyst can eachbe referred to conceptually as separate catalyst beds.

In this discussion, a medium pore dewaxing catalyst refers to a catalystthat includes a 10-member ring molecular sieve. Examples of molecularsieves suitable for forming a medium pore dewaxing catalyst include10-member ring 1-dimensional molecular sieves, such as EU-1, ZSM-35 (orferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23, and ZSM-22.In this discussion, a large pore hydrocracking catalyst refers to acatalyst that includes a 12-member ring molecular sieve. An example of amolecular sieve suitable for forming a large pore hydrocracking catalystis USY zeolite with a silica to alumina ratio of about 200:1 or less anda unit cell size of about 24.5 Angstroms or less.

In this discussion, the distillate boiling range is defined as 350° F.(177° C.) to 700° F. (371° C.). Distillate boiling range products caninclude products suitable for use as kerosene products (including jetfuel products) and diesel products, such as premium diesel or winterdiesel products. Such distillate boiling range products can be suitablefor use directly, or optionally after further processing. With regard toother boiling ranges, the lubricant boiling range is defined as 700° F.(371° C.) to 950° F. (482° C.) and the naphtha boiling range is definedas 100° F. (37° C.) to 350° F. (177° C.).

A wide range of petroleum and chemical feedstocks can be hydroprocessedin accordance with the present disclosure. Some suitable feedstocksinclude gas oils, such as vacuum gas oils. More generally, suitablefeedstocks include whole and reduced petroleum crudes, atmospheric andvacuum residua, solvent deasphalted residua, cycle oils, FCC towerbottoms, gas oils, including atmospheric and vacuum gas oils and cokergas oils, light to heavy distillates including raw virgin distillates,hydrocrackates, hydrotreated oils, dewaxed oils, slack waxes,Fischer-Tropsch waxes, raffinates, and mixtures of these materials.

One way of defining a feedstock is based on the boiling range of thefeed. One option for defining a boiling range is to use an initialboiling point for a feed and/or a final boiling point for a feed.Another option, which in some instances may provide a morerepresentative description of a feed, is to characterize a feed based onthe amount of the feed that boils at one or more temperatures. Forexample, a “T5” boiling point for a feed is defined as the temperatureat which 5 wt % of the feed will boil off. Similarly, a “T95” boilingpoint is a temperature at which 95 wt % of the feed will boil, while a“T99.5” boiling point is a temperature at which 99.5 wt % of the feedwill boil.

Typical feeds include, for example, feeds with an initial boiling pointof at least about 650° F. (343° C.), or at least about 700° F. (371°C.), or at least about 750° F. (399° C.). The amount of lower boilingpoint material in the feed may impact the total amount of dieselgenerated as a side product. Alternatively, a feed may be characterizedusing a T5 boiling point, such as a feed with a T5 boiling point of atleast about 650° F. (343° C.), or at least about 700° F. (371° C.), orat least about 750° F. (399° C.). Typical feeds include, for example,feeds with a final boiling point of about 1150° F. (621° C.), or about1100° F. (593° C.) or less, or about 1050° F. (566° C.) or less.Alternatively, a feed may be characterized using a T95 boiling point,such as a feed with a T95 boiling point of about 1150° F. (621° C.), orabout 1100° F. (593° C.) or less, or about 1050° F. (566° C.) or less.It is noted that feeds with still lower initial boiling points and/or T5boiling points may also be suitable for increasing the yield of premiumdiesel, so long as sufficient higher boiling material is available sothat the overall nature of the process is a lubricant base oilproduction process. Feedstocks such as deasphalted oil with a finalboiling point or a T95 boiling point of about 1150° F. (621° C.) or lessmay also be suitable.

In some aspects, feeds with an increased amount of distillate boilingrange components can be used as feedstocks. Traditionally suchdistillate boiling range components would be excluded from a process forhydrocracking of a gas oil feed, in order to avoid conversion of thedistillate components to less valuable naphtha or light ends products.In such aspects, the T5 boiling point of a feedstock can be at leastabout 473° F. (245° C.), such as at least about 527° F. (275° C.), or atleast about 572° F. (300° C.), or at least about 600° F. (316° C.).

In aspects involving an initial sulfur removal stage prior tohydrocracking, the sulfur content of the feed can be at least about 100ppm by weight of sulfur, or at least about 1000 wppm, or at least about2000 wppm, or at least about 4000 wppm, or at least about 20,000 wppm,such as up to about 40,000 wppm or more. In other embodiments, includingsome embodiments where a previously hydrotreated and/or hydrocrackedfeed is used, the sulfur content can be about 2000 wppm or less, orabout 1000 wppm or less, or about 500 wppm or less, or about 100 wppm orless.

In aspects involving an initial hydroprocessing stage prior tohydrocracking, the nitrogen content of the feed can be at least about 50ppm by weight of nitrogen, or at least about 100 wppm, or at least about500 wppm, or at least about 1000 wppm, or at least about 2500 wppm, suchas up to about 5,000 wppm or more. In other embodiments, including someembodiments where a previously hydrotreated and/or hydrocracked feed isused, the nitrogen content can be about 500 wppm or less, or about 100wppm or less, or about 50 wppm or less, or about 10 wppm or less.

In aspects involving an initial hydroprocessing stage prior tohydrocracking, the aromatics content of the feed can be at least about 5wt % aromatics, or at least about 10 wt %, or at least about 15 wt %, orat least about 20 wt %, or at least about 25 wt %, such as up to about30 wt % or more. In other embodiments, including some embodiments wherea previously hydrotreated and/or hydrocracked feed is used, thearomatics content can be about 15 wt % or less, or about 10 wt % orless, or about 5 wt % or less, or about 1 wt % or less.

In some aspects, at least a portion of the feed can correspond to a feedderived from a biocomponent source. In this discussion, a biocomponentfeedstock refers to a hydrocarbon feedstock derived from a biologicalraw material component, from biocomponent sources such as vegetable,animal, fish, and/or algae. Note that, for the purposes of thisdocument, vegetable fats/oils refer generally to any plant basedmaterial, and can include fat/oils derived from a source such as plantsof the genus Jatropha. Generally, the biocomponent sources can includevegetable fats/oils, animal fats/oils, fish oils, pyrolysis oils, andalgae lipids/oils, as well as components of such materials, and in someembodiments can specifically include one or more type of lipidcompounds. Lipid compounds are typically biological compounds that areinsoluble in water, but soluble in nonpolar (or fat) solvents.Non-limiting examples of such solvents include alcohols, ethers,chloroform, alkyl acetates, benzene, and combinations thereof.

Hydrotreatment Conditions

In various aspects, hydrotreating of a feed can be performed by exposingthe feed to a catalyst formed from a suitable precursor, as describedbelow, in the presence of hydrogen. A hydrogen stream is, therefore, fedor injected into a vessel or reaction zone or hydroprocessing zone inwhich the hydroprocessing catalyst is located. Hydrogen, which iscontained in a hydrogen-containing “treat gas,” is provided to thereaction zone. Treat gas, as referred to in this disclosure, can beeither pure hydrogen or a hydrogen-containing gas, which is a gas streamcontaining hydrogen in an amount that is sufficient for the intendedreaction(s), optionally including one or more other gasses (e.g.,nitrogen and light hydrocarbons such as methane), and which will notadversely interfere with or affect either the reactions or the products.Impurities, such as H₂S and NH₃ are undesirable and would typically beremoved from the treat gas before it is conducted to the reactor. Thetreat gas stream introduced into a reaction stage will preferablycontain at least about 50 vol. % and more preferably at least about 75vol. % hydrogen.

Hydrotreating conditions can include temperatures of about 200° C. toabout 450° C., or about 315° C. to about 425° C.; pressures of about 250psig (1.8 MPag) to about 5000 psig (34.6 MPag) or about 300 psig (2.1MPag) to about 3000 psig (20.8 MPag); liquid hourly space velocities(LHSV) of about 0.1 hr⁻¹ to about 10 hr⁻¹; and hydrogen treat rates ofabout 200 scf/B (35.6 m³/m³) to about 10,000 scf/B (1781 m³/m³), orabout 500 (89 m³/m³) to about 10,000 scf/B (1781 m³/m³).

Optionally, the hydrotreatment can be performed using a mixture of thecatalyst formed from a suitable precursor and a conventionalhydrotreating catalyst, such as those that comprise at least one GroupVIII non-noble metal (Columns 8-10 of IUPAC periodic table), preferablyFe, Co, and/or Ni, such as Co and/or Ni; and at least one Group VI metal(Column 6 of IUPAC periodic table), preferably Mo and/or W. Suchhydroprocessing catalysts can optionally include transition metalsulfides. These metals or mixtures of metals are typically present asoxides or sulfides on refractory metal oxide supports. Suitable metaloxide supports include low acidic oxides such as silica, alumina,titania, silica-titania, and titania-alumina. Suitable aluminas areporous aluminas such as gamma or eta having average pore sizes from 50to 200 Å, or 75 to 150 Å; a surface area from 100 to 300 m²/g, or 150 to250 m²/g; and a pore volume of from 0.25 to 1.0 cm³/g, or 0.35 to 0.8cm³/g. The supports are preferably not promoted with a halogen such asfluorine as this generally increases the acidity of the support.

The at least one Group VIII non-noble metal, in oxide form, cantypically be present in an amount ranging from about 2 wt % to about 40wt %, preferably from about 4 wt % to about 15 wt %. The at least oneGroup VI metal, in oxide form, can typically be present in an amountranging from about 2 wt % to about 70 wt %, preferably for supportedcatalysts from about 6 wt % to about 40 wt % or from about 10 wt % toabout 30 wt %. These weight percents are based on the total weight ofthe catalyst. Suitable metal catalysts include cobalt/molybdenum (1-10%Co as oxide, 10-40% Mo as oxide), nickel/molybdenum (1-10% Ni as oxide,10-40% Co as oxide), or nickel/tungsten (1-10% Ni as oxide, 10-40% W asoxide) on alumina, silica, silica-alumina, or titania.

Alternatively, the hydrotreating catalyst can be a bulk metal catalyst,or a combination of stacked beds of supported and bulk metal catalyst.By bulk metal, it is meant that the catalysts are unsupported whereinthe bulk catalyst particles comprise 30-100 wt. % of at least one GroupVIII non-noble metal and at least one Group VIB metal, based on thetotal weight of the bulk catalyst particles, calculated as metal oxidesand wherein the bulk catalyst particles have a surface area of at least10 m²/g. It is furthermore preferred that the bulk metal hydrotreatingcatalysts used herein comprise about 50 to about 100 wt %, and even morepreferably about 70 to about 100 wt %, of at least one Group VIIInon-noble metal and at least one Group VIB metal, based on the totalweight of the particles, calculated as metal oxides. The amount of GroupVIB and Group VIII non-noble metals can easily be determined VIBTEM-EDX.

Bulk catalyst compositions comprising one Group VIII non-noble metal andtwo Group VIB metals are preferred. It has been found that in this case,the bulk catalyst particles are sintering-resistant. Thus the activesurface area of the bulk catalyst particles is maintained during use.The molar ratio of Group VIB to Group VIII non-noble metals rangesgenerally from 10:1-1:10 and preferably from 3:1-1:3. In the case of acore-shell structured particle, these ratios of course apply to themetals contained in the shell. If more than one Group VIB metal iscontained in the bulk catalyst particles, the ratio of the differentGroup VIB metals is generally not critical. The same holds when morethan one Group VIII non-noble metal is applied. In the case wheremolybdenum and tungsten are present as Group VIB metals, themolybdenum:tungsten ratio preferably lies in the range of 9:1-1:9.Preferably the Group VIII non-noble metal comprises nickel and/orcobalt. It is further preferred that the Group VIB metal comprises acombination of molybdenum and tungsten. Preferably, combinations ofnickel/molybdenum/tungsten and cobalt/molybdenum/tungsten andnickel/cobalt/molybdenum/tungsten are used. These types of precipitatesappear to be sinter-resistant. Thus, the active surface area of theprecipitate is maintained during use. The metals are preferably presentas oxidic compounds of the corresponding metals, or if the catalystcomposition has been sulfided, sulfidic compounds of the correspondingmetals.

It is also preferred that the bulk metal hydrotreating catalysts usedherein have a surface area of at least 50 m²/g and more preferably of atleast 100 m²/g. It is also desired that the pore size distribution ofthe bulk metal hydrotreating catalysts be approximately the same as theone of conventional hydrotreating catalysts. Bulk metal hydrotreatingcatalysts have a pore volume of 0.05-5 ml/g, or of 0.1-4 ml/g, or of0.1-3 ml/g, or of 0.1-2 ml/g determined by nitrogen adsorption.Preferably, pores smaller than 1 nm are not present. The bulk metalhydrotreating catalysts can have a median diameter of at least 50 nm, orat least 100 nm. The bulk metal hydrotreating catalysts can have amedian diameter of not more than 5000 μm, or not more than 3000 μm. Inan embodiment, the median particle diameter lies in the range of 0.1-50μm and most preferably in the range of 0.5-50 μm.

Hydrocracking Conditions

Hydrocracking catalysts typically contain sulfided base metals on acidicsupports, such as amorphous silica alumina, cracking zeolites or othercracking molecular sieves such as USY, or acidified alumina. In somepreferred aspects, a hydrocracking catalyst can include at least onemolecular sieve, such as a zeolite. Often these acidic supports aremixed or bound with other metal oxides such as alumina, titania orsilica. Non-limiting examples of supported catalytic metals forhydrocracking catalysts include nickel, nickel-cobalt-molybdenum,cobalt-molybdenum, nickel-tungsten, nickel-molybdenum, and/ornickel-molybdenum-tungsten. Additionally or alternately, hydrocrackingcatalysts with noble metals can also be used. Non-limiting examples ofnoble metal catalysts include those based on platinum and/or palladium.Support materials which may be used for both the noble and non-noblemetal catalysts can comprise a refractory oxide material such asalumina, silica, alumina-silica, kieselguhr, diatomaceous earth,magnesia, zirconia, or combinations thereof, with alumina, silica,alumina-silica being the most common (and preferred, in one embodiment).

In some aspects, a hydrocracking catalyst can include a large poremolecular sieve that is selective for cracking of branched hydrocarbonsand/or cyclic hydrocarbons. Zeolite Y, such as ultrastable zeolite Y(USY) is an example of a zeolite molecular sieve that is selective forcracking of branched hydrocarbons and cyclic hydrocarbons. Depending onthe aspect, the silica to alumina ratio in a USY zeolite can be at leastabout 10, such as at least about 15, or at least about 25, or at leastabout 50, or at least about 100. Depending on the aspect, the unit cellsize for a USY zeolite can be about 24.50 Angstroms or less, such asabout 24.45 Angstroms or less, or about 24.40 Angstroms or less, orabout 24.35 Angstroms or less, such as about 24.30 Angstroms.

In various embodiments, the conditions selected for hydrocracking candepend on the desired level of conversion, the level of contaminants inthe input feed to the hydrocracking stage, and potentially otherfactors. A hydrocracking process performed under sour conditions, suchas conditions where the sulfur content of the input feed to thehydrocracking stage is at least 500 wppm, can be carried out attemperatures of about 550° F. (288° C.) to about 840° F. (449° C.),hydrogen partial pressures of from about 250 psig to about 5000 psig(1.8 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05 h⁻¹to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to 1781 m³/m³(200 SCF/B to 10,000 SCF/B). In other embodiments, the conditions caninclude temperatures in the range of about 600° F. (343° C.) to about815° F. (435° C.), hydrogen partial pressures of from about 500 psig toabout 3000 psig (3.5 MPag-20.9 MPag), liquid hourly space velocities offrom about 0.2 h⁻¹ to about 2 h⁻¹ and hydrogen treat gas rates of fromabout 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000 SCF/B).

A hydrocracking process performed under non-sour conditions can beperformed under conditions similar to those used for sour conditions, orthe conditions can be different. Alternatively, a non-sour hydrocrackingstage can have less severe conditions than a similar hydrocracking stageoperating under sour conditions. Suitable hydrocracking conditions caninclude temperatures of about 550° F. (288° C.) to about 840° F. (449°C.), hydrogen partial pressures of from about 250 psig to about 5000psig (1.8 MPag to 34.6 MPag), liquid hourly space velocities of from0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to1781 m³/m³ (200 SCF/B to 10,000 SCF/B). In other embodiments, theconditions can include temperatures in the range of about 600° F. (343°C.) to about 815° F. (435° C.), hydrogen partial pressures of from about500 psig to about 3000 psig (3.5 MPag-20.9 MPag), liquid hourly spacevelocities of from about 0.2 h⁻¹ to about 2 h⁻¹ and hydrogen treat gasrates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000SCF/B).

Dewaxing Process

In various embodiments, a dewaxing catalyst is also included. Typically,the dewaxing catalyst is located in a bed downstream from anyhydrocracking catalyst stages and/or any hydrocracking catalyst presentin a stage. This can allow the dewaxing to occur on molecules that havealready been hydrotreated or hydrocracked to remove a significantfraction of organic sulfur- and nitrogen-containing species. Thedewaxing catalyst can be located in the same reactor as at least aportion of the hydrocracking catalyst in a stage. Alternatively, theeffluent from a reactor containing hydrocracking catalyst, possiblyafter a gas-liquid separation, can be fed into a separate stage orreactor containing the dewaxing catalyst.

Suitable dewaxing catalysts can include molecular sieves such ascrystalline aluminosilicates (zeolites). In an embodiment, the molecularsieve can comprise, consist essentially of, or be ZSM-5, ZSM-22, ZSM-23,ZSM-35, ZSM-48, zeolite Beta, ZSM-57, or a combination thereof, forexample ZSM-23 and/or ZSM-48, or ZSM-48 and/or zeolite Beta. Optionallybut preferably, molecular sieves that are selective for dewaxing byisomerization as opposed to cracking can be used, such as ZSM-48,zeolite Beta, ZSM-23, or a combination thereof. Additionally oralternately, the molecular sieve can comprise, consist essentially of,or be a 10-member ring 1-D molecular sieve. Examples include EU-1,ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23,and ZSM-22. Preferred materials are EU-2, EU-11, ZBM-30, ZSM-48, orZSM-23. ZSM-48 is most preferred. Note that a zeolite having the ZSM-23structure with a silica to alumina ratio of from about 20:1 to about40:1 can sometimes be referred to as SSZ-32. Other molecular sieves thatare isostructural with the above materials include Theta-1, NU-10,EU-13, KZ-1, and NU-23. Optionally but preferably, the dewaxing catalystcan include a binder for the molecular sieve, such as alumina, titania,silica, silica-alumina, zirconia, or a combination thereof, for examplealumina and/or titania or silica and/or zirconia and/or titania.

Preferably, the dewaxing catalysts used in processes according to thedisclosure are catalysts with a low ratio of silica to alumina. Forexample, for ZSM-48, the ratio of silica to alumina in the zeolite canbe less than 200:1, or less than 110:1, or less than 100:1, or less than90:1, or less than 80:1. In various embodiments, the ratio of silica toalumina can be from 30:1 to 200:1, 60:1 to 110:1, or 70:1 to 100:1.

In various embodiments, the catalysts according to the disclosurefurther include a metal hydrogenation component. The metal hydrogenationcomponent is typically a Group VI and/or a Group VIII metal. Preferably,the metal hydrogenation component is a Group VIII noble metal.Preferably, the metal hydrogenation component is Pt, Pd, or a mixturethereof. In an alternative preferred embodiment, the metal hydrogenationcomponent can be a combination of a non-noble Group VIII metal with aGroup VI metal. Suitable combinations can include Ni, Co, or Fe with Moor W, preferably Ni with Mo or W.

The metal hydrogenation component may be added to the catalyst in anyconvenient manner. One technique for adding the metal hydrogenationcomponent is by incipient wetness. For example, after combining azeolite and a binder, the combined zeolite and binder can be extrudedinto catalyst particles. These catalyst particles can then be exposed toa solution containing a suitable metal precursor. Alternatively, metalcan be added to the catalyst by ion exchange, where a metal precursor isadded to a mixture of zeolite (or zeolite and binder) prior toextrusion.

The amount of metal in the catalyst can be at least 0.1 wt % based oncatalyst, or at least 0.15 wt %, or at least 0.2 wt %, or at least 0.25wt %, or at least 0.3 wt %, or at least 0.5 wt % based on catalyst. Theamount of metal in the catalyst can be 20 wt % or less based oncatalyst, or 10 wt % or less, or 5 wt % or less, or 2.5 wt % or less, or1 wt % or less. For embodiments where the metal is Pt, Pd, another GroupVIII noble metal, or a combination thereof, the amount of metal can befrom 0.1 to 5 wt %, preferably from 0.1 to 2 wt %, or 0.25 to 1.8 wt %,or 0.4 to 1.5 wt %. For embodiments where the metal is a combination ofa non-noble Group VIII metal with a Group VI metal, the combined amountof metal can be from 0.5 wt % to 20 wt %, or 1 wt % to 15 wt %, or 2.5wt % to 10 wt %.

The dewaxing catalysts useful in processes according to the disclosurecan also include a binder. In some embodiments, the dewaxing catalystsused in process according to the disclosure are formulated using a lowsurface area binder, a low surface area binder represents a binder witha surface area of 100 m²/g or less, or 80 m²/g or less, or 70 m²/g orless.

A zeolite can be combined with binder in any convenient manner. Forexample, a bound catalyst can be produced by starting with powders ofboth the zeolite and binder, combining and mulling the powders withadded water to form a mixture, and then extruding the mixture to producea bound catalyst of a desired size. Extrusion aids can also be used tomodify the extrusion flow properties of the zeolite and binder mixture.The amount of framework alumina in the catalyst may range from 0.1 to3.33 wt %, or 0.1 to 2.7 wt %, or 0.2 to 2 wt %, or 0.3 to 1 wt %.

In yet another embodiment, a binder composed of two or more metal oxidescan also be used. In such an embodiment, the weight percentage of thelow surface area binder is preferably greater than the weight percentageof the higher surface area binder. Alternatively, if both metal oxidesused for forming a mixed metal oxide binder have a sufficiently lowsurface area, the proportions of each metal oxide in the binder are lessimportant. When two or more metal oxides are used to form a binder, thetwo metal oxides can be incorporated into the catalyst by any convenientmethod. For example, one binder can be mixed with the zeolite duringformation of the zeolite powder, such as during spray drying. The spraydried zeolite/binder powder can then be mixed with the second metaloxide binder prior to extrusion. In yet another embodiment, the dewaxingcatalyst is self-bound and does not contain a binder.

A bound dewaxing catalyst can also be characterized by comparing themicropore (or zeolite) surface area of the catalyst with the totalsurface area of the catalyst. These surface areas can be calculatedbased on analysis of nitrogen porosimetry data using the BET method forsurface area measurement. Previous work has shown that the amount ofzeolite content versus binder content in catalyst can be determined fromBET measurements (see, e.g., Johnson, M. F. L., Jour. Catal., (1978) 52,425). The micropore surface area of a catalyst refers to the amount ofcatalyst surface area provided due to the molecular sieve and/or thepores in the catalyst in the BET measurements. The total surface arearepresents the micropore surface plus the external surface area of thebound catalyst. In one embodiment, the percentage of micropore surfacearea relative to the total surface area of a bound catalyst can be atleast about 35%, for example at least about 38%, at least about 40%, orat least about 45%. Additionally or alternately, the percentage ofmicropore surface area relative to total surface area can be about 65%or less, for example about 60% or less, about 55% or less, or about 50%or less.

Additionally or alternately, the dewaxing catalyst can comprise, consistessentially of, or be a catalyst that has not been dealuminated. Furtheradditionally or alternately, the binder for the catalyst can include amixture of binder materials containing alumina.

Process conditions in a catalytic dewaxing zone can include atemperature of about 200° C. to about 450° C., preferably about 270° C.to about 400° C., a hydrogen partial pressure of about 1.8 MPag to about34.6 MPag (250 psig to 5000 psig), preferably about 4.8 MPag to about20.8 MPag, and a hydrogen treat gas rate of about 35.6 m³/m³ (200 SCF/B)to about 1781 m³/m³ (10,000 scf/B), preferably about 178 m³/m³ (1000SCF/B) to about 890.6 m³/m³ (5000 SCF/B). In still other embodiments,the conditions can include temperatures in the range of about 600° F.(343° C.) to about 815° F. (435° C.), hydrogen partial pressures of fromabout 500 psig to about 3000 psig (3.5 MPag-20.9 MPag), and hydrogentreat gas rates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF.The LHSV can be from about 0.1 h⁻¹ to about 10 h⁻¹, such as from about0.5 h⁻¹ to about 5 h⁻¹ and/or from about 1 h⁻¹ to about 4 h⁻¹.

Hydrofinishing and/or Aromatic Saturation Process

In various embodiments, a hydrofinishing, an aromatic saturation stage,or a hydrofinishing and an aromatic saturation stage may also beprovided. The hydrofinishing and/or aromatic saturation stage(s) orreaction zones can occur after the last hydrocracking or dewaxing stage.The hydrofinishing and/or aromatic saturation can occur either before orafter fractionation. If hydrofinishing and/or aromatic saturation occursafter fractionation, the hydrofinishing can be performed on one or moreportions of the fractionated product, such as being performed on one ormore lubricant base oil portions. Alternatively, the entire effluentfrom the last hydrocracking or dewaxing process can be hydrofinishedand/or undergo aromatic saturation.

In some situations, a hydrofinishing process and an aromatic saturationprocess can refer to a single process performed using the same catalyst.Alternatively, one type of catalyst or catalyst system can be providedto perform aromatic saturation, while a second catalyst or catalystsystem can be used for hydrofinishing. As still another alternative,aromatic saturation sometimes refers to a higher temperature range ofprocessing than a hydrofinishing process. In such an alternative, ahydrofinishing process may be suitable for removing (for example) colorbodies from a product, but otherwise result in a lower amount ofaromatic saturation than an aromatic saturation process. Typically ahydrofinishing and/or aromatic saturation process will be performed in aseparate reactor from dewaxing or hydrocracking processes for practicalreasons, such as facilitating use of a lower temperature for thehydrofinishing or aromatic saturation process. However, an additionalhydrofinishing reactor following a hydrocracking or dewaxing process butprior to fractionation could still be considered part of a second stageof a reaction system conceptually.

Hydrofinishing and/or aromatic saturation catalysts can includecatalysts containing Group VI metals, Group VIII metals, and mixturesthereof. In an embodiment, preferred metals include at least one metalsulfide having a strong hydrogenation function. In another embodiment,the hydrofinishing catalyst can include a Group VIII noble metal, suchas Pt, Pd, or a combination thereof. The mixture of metals may also bepresent as bulk metal catalysts wherein the amount of metal is about 30wt. % or greater based on catalyst. Suitable metal oxide supportsinclude low acidic oxides such as silica, alumina, silica-aluminas ortitania, preferably alumina. The preferred hydrofinishing catalysts foraromatic saturation can comprise at least one metal having relativelystrong hydrogenation function on a porous support. The support materialsmay also be modified, such as by halogenation, or in particularfluorination. The metal content of the catalyst is often as high asabout 20 weight percent for non-noble metals. In some optional aspects,hydrotreating catalysts as described above can be used as hydrotreatingcatalysts. In other optional aspects, a preferred hydrofinishingcatalyst can include a crystalline material belonging to the M41S classor family of catalysts. The M41S family of catalysts are mesoporousmaterials having high silica content. Examples include MCM-41, MCM-48and MCM-50. A preferred member of this class is MCM-41. If separatecatalysts are used for aromatic saturation and hydrofinishing, anaromatic saturation catalyst can be selected based on activity and/orselectivity for aromatic saturation, while a hydrofinishing catalyst canbe selected based on activity for improving product specifications, suchas product color and polynuclear aromatic reduction.

Hydrofinishing conditions can include temperatures from about 125° C. toabout 425° C., preferably about 180° C. to about 280° C., totalpressures from about 500 psig (3.4 MPa) to about 3000 psig (20.7 MPa),preferably about 1500 psig (10.3 MPa) to about 2500 psig (17.2 MPa), andliquid hourly space velocity from about 0.1 hr⁻¹ to about 5 hr⁻¹ LHSV,preferably about 0.5 hr⁻¹ to about 1.5 hr⁻¹.

In aspects where aromatic saturation is contemplated as a distinctprocess from hydrofinishing, aromatic saturation conditions can includetemperatures from about 175° C. to about 425° C., or about 200° C. toabout 425° C., preferably about 225° C. to about 325° C., or about 225°C. to about 280° C., total pressures from about 500 psig (3.4 MPa) toabout 3000 psig (20.7 MPa), preferably about 1500 psig (10.3 MPa) toabout 2500 psig (17.2 MPa), and liquid hourly space velocity from about0.1 hr⁻¹ to about 5 hr⁻¹ LHSV, preferably about 0.5 hr⁻¹ to about 1.5hr⁻¹.

Alternative Process Configurations and Uses for Catalyst Formed from aSuitable Precursor

In addition to the process configuration described above, a catalystcomposition derived from a suitable precursor, as described herein, canbe used in a variety of hydroprocessing processes to treat a pluralityof feeds under wide-ranging reaction conditions such as temperatures offrom 200 to 450° C., hydrogen pressures of from 5 to 300 bar, liquidhourly space velocities of from 0.05 to 10 h⁻¹ and hydrogen treat gasrates of from 35.6 to 1780 m³/m³ (200 to 10000 SCF/B). The term“hydroprocessing” encompasses all processes in which a hydrocarbon feedis reacted with hydrogen at the temperatures and pressures noted above,and include hydrogenation, hydrotreating, hydrodesulfurization,hydrodenitrogenation, hydrodemetallation, hydrodearomatization,hydroisomerization, hydrodewaxing, and hydrocracking including selectivehydrocracking. Depending on the type of hydroprocessing and the reactionconditions, the products of hydroprocessing may show improvedviscosities, viscosity indices, saturates content, low temperatureproperties, volatilities and depolarization. Feeds for hydroprocessinginclude reduced crudes, hydrocrackates, raffinates, hydrotreated oils,atmospheric and vacuum gas oils, coker gas oils, atmospheric and vacuumresids, deasphalted oils, dewaxed oils, slack waxes, Fischer-Tropschwaxes and mixtures thereof. It is to be understood that hydroprocessingof the present disclosure can be practiced in one or more reaction zonesand can be practiced in either countercurrent flow or cocurrent flowmode. By countercurrent flow mode we mean a process mode wherein thefeedstream flows countercurrent to the flow of hydrogen-containing treatgas.

A catalyst composition derived from a suitable precursor can beparticularly suitable for hydrotreating the hydrocarbon feeds suitablefor hydroprocessing as noted above. Examples of hydrotreating includehydrogenation of unsaturates, hydrodesulfurization,hydrodenitrogenation, hydrodearomatization and mild hydrocracking.Conventional hydrotreating conditions include temperatures of from 250°C. to 450° C., hydrogen pressures of from 5 to 250 bar, liquid hourlyspace velocities of from 0.1 to 10 h⁻¹, and hydrogen treat gas rates offrom 90 to 1780 m³/m³ (500 to 10000 SCF/B). The hydrotreating processesusing the catalyst according to the disclosure may be particularlysuitable for making lubricating oil basestocks meeting Group II or GroupIII base oil requirements.

A wide range of petroleum and chemical feedstocks can be hydroprocessedin accordance with this type of aspect. Suitable feedstocks range fromthe relatively light distillate fractions up to high boiling stocks suchas whole crude petroleum, reduced crudes, vacuum tower residua, propanedeasphalted residua, e.g., brightstock, cycle oils, FCC tower bottoms,gas oils including coker gas oils and vacuum gas oils, deasphaltedresidua and other heavy oils. The feedstock will normally be a C.sub.10+feedstock, since light oils will usually be free of significantquantities of waxy components. However, the process is also particularlyuseful with waxy distillate stocks, such as gas oils, kerosenes, jetfuels, lubricating oil stocks, heating oils, hydrotreated oil stock,furfural-extracted lubricating oil stock and other distillate fractionswhose pour point and viscosity properties need to be maintained withincertain specification limits. Lubricating oil stocks, for example, willgenerally boil above 230° C. and more usually above 315° C. For purposesof this disclosure, lubricating oil or lube oil is that part of thehydrocarbon feedstock having a boiling point of at least 315° C., asdetermined by ASTM D-1160 test method.

In some aspects, a feed can be exposed to a catalyst derived from asuitable precursor under effective conditions for performing ahydroconversion process. The hydroconversion process can be part of aseries or group of processes for producing a lubricant base stock. Forexample, a hydroconversion process can be used to produce a lubricatingoil basestock meeting at least 90% saturates and VI of at least 105 byselectively hydroconverting a raffinate produced from solvent refining alubricating oil feedstock. The solvent extraction process selectivelydissolves the aromatic components in an extract phase while leaving themore paraffinic components in a raffinate phase. Naphthenes aredistributed between the extract and raffinate phases. Typical solventsfor solvent extraction include phenol, furfural and N-methylpyrrolidone. By controlling the solvent to oil ratio, extractiontemperature and method of contacting distillate to be extracted withsolvent, one can control the degree of separation between the extractand raffinate phases. The raffinate from the solvent extraction ispreferably under-extracted, i.e., the extraction is carried out underconditions such that the raffinate yield is maximized while stillremoving most of the lowest quality molecules from the feed. Raffinateyield may be maximized by controlling extraction conditions, forexample, by lowering the solvent to oil treat ratio and/or decreasingthe extraction temperature. The raffinate from the solvent extractionunit is stripped of solvent and then sent to a first hydroconversionunit containing a hydroconversion catalyst. This raffinate feed has aviscosity index of from about 80 to about 105 and a boiling range not toexceed about 650° C., preferably less than 600° C., as determined byASTM 2887 and a viscosity of from 3 to 15 cSt at 100° C. The strippedraffinate from the solvent extraction zone may be solvent dewaxed priorto being sent to the first hydroconversion unit.

The raffinate feed is passed to a first hydroconversion zone andprocessed in the presence of the catalyst derived from a suitableprecursor under hydroconversion conditions to produce a firsthydroconverted raffinate. The hydroconverted raffinate from the firsthydroconversion zone may then be passed to a hydrofinishing zone or inthe alternative passed to a second hydroconversion zone and then passedto a hydrofinishing zone. In the case of two hydroconversion zones, thecatalyst in both hydroconversion zones may be a catalyst derived from asuitable precursor, or the catalyst derived from a suitable precursormay be used in either the first or second hydroconversion zones. In thecase of two zones where the catalyst derived from a suitable precursoris used in only one of the zones, the other catalyst may be a differenttype of bulk or supported hydrotreating catalyst. Hydrotreatingcatalysts are those containing at least one Group VIB and at least oneGroup VIII metal supported on a refractory metal oxide. For typicalalternative hydrotreating catalysts for use in this aspect, the GroupVIB metal is preferably molybdenum or tungsten and the Group VIII metalis preferably a non-noble metal such as cobalt or nickel.

The hydroconversion conditions in either the first or secondhydroconversion zones include temperatures of from 250 to 420° C.,hydrogen pressures of from 300 to 3000 psig (2170 to 20786 kPa), liquidhourly space velocities of from 0.1 to 10 and hydrogen treat gas ratesof from 500 to 5000 scf/B (89 to 890 m³/m³).

The hydroconversion zone(s) are then followed by a hydrofinishing zone.The hydrofinishing zone corrects product quality properties such ascolor, stability and toxicity. The hydrofinishing zone is characterizedas a cold hydrofinishing zone with conditions including temperatures offrom 150 to 360° C., hydrogen pressures of from 300 to 3000 psig (2170to 20786 kPa), liquid hourly space velocities of from 0.1 to 10 hr⁻¹ andhydrogen treat gas rates of from 500 to 5000 scf/B (89 to 890 m³/m³).The catalyst for the hydrofinishing zone may be either the bulk metalcatalyst according to the disclosure or may be a non-bulk metalhydrotreating catalyst. Hydrotreating catalysts are those containing atleast one Group VIB and at least one Group VIII metal supported on arefractory metal oxide. The Group VIB metal is preferably molybdenum ortungsten and the Group VIII metal is preferably a non-noble metal suchas cobalt or nickel.

The hydrofinishing zone may be preceded by or followed by a dewaxingzone. The dewaxing may be either catalytic or solvent. Solvent dewaxingmay be accomplished by using a solvent and chilling to crystallize andseparate wax molecules. Typical solvents include propane and ketones.Preferred ketones include methyl ethyl ketone, methyl isobutyl ketoneand mixtures thereof. Catalytic dewaxing may be accomplished using an 8,10 or 12 ring molecular sieve. Preferred molecular sieves includezeolites and silicoaluminophosphates (SAPOs). 10 ring molecular sievesare preferred including at least one of ZSM-5, ZSM-22, ZSM-23, ZSM-35,ZSM-48 ZSM-57, SAPO-11, and SAPO-41.

The hydrocarbon feedstocks which are typically subjected tohydroconversion herein will typically boil at a temperature above 150°C. The feedstocks can contain a substantial amount of nitrogen, e.g. atleast 10 wppm nitrogen, and even greater than 500 wppm, in the form oforganic nitrogen compounds. The feeds can also have a significant sulfurcontent, ranging from about 0.1 wt. % to 3 wt. %, or higher. If desired,the feeds can be treated in a known or conventional manner to reduce thesulfur and/or nitrogen content thereof.

For purposes of the present disclosure where it is desirable to producea lube basestock the feed can be a wide variety of wax-containingfeedstocks including feeds derived from crude oils, shale oils and tarsands as well as synthetic feeds such as those derived from theFischer-Tropsch process. Typical wax-containing feedstocks for thepreparation of lubricating base oils have initial boiling points ofabout 315° C. or higher, and include feeds such as reduced crudes,hydrocrackates, raffinates, hydrotreated oils, atmospheric gas oils,vacuum gas oils, coker gas oils, atmospheric and vacuum resids,deasphalted oils, slack waxes and Fischer-Tropsch wax. The feed ispreferably a mixture of gas oil from a coker and vacuum distillationfrom conventional crudes with a maximum boiling point of the coker gasoil not to exceed 1050° F. Such feeds may be derived from distillationtowers (atmospheric and vacuum), hydrocrackers, hydrotreaters andsolvent extraction units, and may have wax contents of up to 50% ormore.

Hydroprocessing of the present disclosure also includes slurry andebullating bed hydrotreating processes for the removal of sulfur andnitrogen compounds and the hydrogenation of aromatic molecules presentin light fossil fuels such as petroleum mid-distillates. Hydrotreatingprocesses utilizing a slurry of dispersed catalysts in admixture with ahydrocarbon oil are generally known. For example, U.S. Pat. No.4,557,821 to Lopez et al discloses hydrotreating a heavy oil employing acirculating slurry catalyst. Other patents disclosing slurryhydrotreating include U.S. Pat. Nos. 3,297,563; 2,912,375; and2,700,015. The slurry hydroprocessing process of this disclosure can beused to treat various feeds including mid-distillates from fossil fuelssuch as light catalytic cycle cracking oils (LCCO). Distillates derivedfrom petroleum, coal, bitumen, tar sands, or shale oil are likewisesuitable feeds. On the other hand, the present process is not useful fortreating heavy catalytic cracking cycle oils (HCCO), coker gas oils,vacuum gas oils (VGO) and heavier resids, which contain several percent3+ ring aromatics, particularly large asphaltenic molecules. Whentreating heavier resids, excess catalyst sites are not obtainable, andreactivation of the catalyst by high temperature denitrogenation is notfeasible.

The present disclosure can also be used to produce white oils. Whitemineral oils, called white oils, are colorless, transparent, oilyliquids obtained by the refining of crude petroleum feedstocks. In theproduction of white oils, an appropriate petroleum feedstock is refinedto eliminate, as completely as possible, oxygen, nitrogen, and sulfurcompounds, reactive hydrocarbons including aromatics, and any otherimpurity which would prevent use of the resulting white oil in thepharmaceutical or food industry.

In still other aspects, a catalyst derived from a suitable precursor canbe used for hydrofining of hydrocarbon and/or hydrocarbonaceousfeedtocks to The hydrocarbon feedstocks which are typically subjected tohydrofining herein will typically boil at a temperature above 150 C.Examples of hydrocarbon feedstocks are those derived from at least oneof thermal treatment, catalytic treatment, solvent extraction, dewaxingor fractionation of a petroleum crude or fraction thereof, shale oil,tar sand or synthetic crude. Preferred feeds are waxy or dewaxed vacuumgas oil distillates, waxy or dewaxed hydrotreated or hydrocracked vacuumgas oil distillates, waxy or dewaxed solvent extracted raffinates andwaxes boiling above 315° C.

The hydrocarbon feedstocks are typically subjected to hydrofining toremove nitrogen- and sulfur-containing compounds as well as remove othercontaminants such as those which cause unfavorable color and stabilityproperties as well as any solvents remaining in the feedstock from priorsolvent extraction steps. Hydrofining conditions include temperatures offrom 200 to 400° C., hydrogen pressures of from 150 to 3500 psig (1136to 24234 kPa), liquid hourly space velocities of from 0.5 to 5 andhydrogen treat gas rates of from 100 to 5000 scf/B (17.8 to 890 m³/m³).

The hydrofining catalyst may also contain, in addition to the catalystderived from a suitable precursor, from 5 to 95 wt. %, based onhydrofining catalyst, of a non-bulk metal, hydrotreating catalystcontaining at least one Group VIB and at least one non-noble metal GroupVIII metal on a refractory oxide support. The preferred hydrotreatingcatalyst comprises at least one of molybdenum and tungsten and at leastone of cobalt and nickel on a metal oxide support such as silica,alumina and silica-alumina. The hydrofining catalyst may containmixtures of the catalyst derived from a suitable precursor andhydrotreating catalyst. Alternatively, the catalyst derived from asuitable precursor and hydrotreating catalyst may be in separate beds,either in a single reactor or in separate reactors.

For purposes of the present disclosure where it is desirable to producea lube basestock the feed can be a wide variety of wax-containingfeedstocks including feeds derived from crude oils, shale oils and tarsands as well as synthetic feeds such as those derived from theFischer-Tropsch process. Typical wax-containing feedstocks for thepreparation of lubricating base oils have initial boiling points ofabout 315° C. or higher, and include feeds such as reduced crudes,hydrocrackates, raffinates, hydrotreated oils, atmospheric gas oils,vacuum gas oils, coker gas oils, atmospheric and vacuum resids,deasphalted oils, slack waxes and Fischer-Tropsch wax. The feed ispreferably a mixture of gas oil from a coker and vacuum distillationfrom conventional crudes with a maximum boiling point of the coker gasoil not to exceed 1050° F. Such feeds may be derived from distillationtowers (atmospheric and vacuum), hydrocrackers, hydrotreaters andsolvent extraction units, and may have wax contents of up to 50% ormore.

In yet other aspects, a catalyst derived from a suitable precursor canbe used for hydrocracking of a feed as part of a process for producing alubricant oil basestock. A wide range of petroleum and chemicalfeedstocks can be hydroprocessed in accordance with the presentdisclosure. Suitable feedstocks range from the relatively lightdistillate fractions up to high boiling stocks such as whole crudepetroleum, reduced crudes, vacuum tower residua, propane deasphaltedresidua, e.g., brightstock, cycle oils, FCC tower bottoms, gas oilsincluding coker gas oils and vacuum gas oils, deasphalted residua andother heavy oils. The feedstock will normally be a C.sub.10+ feedstock,since light oils will usually be free of significant quantities of waxycomponents. However, the process is also particularly useful with waxydistillate stocks, such as gas oils, kerosenes, jet fuels, lubricatingoil stocks, heating oils, hydrotreated oil stock, furfural-extractedlubricating oil stock and other distillate fractions whose pour pointand viscosity properties need to be maintained within certainspecification limits. Lubricating oil stocks, for example, willgenerally boil above 230° C. and more usually above 315° C. For purposesof this disclosure, lubricating oil or lube oil is that part of thehydrocarbon feedstock having a boiling point of at least 315° C., asdetermined by ASTM D-1160 test method.

The hydrocarbon feedstocks which are typically subjected tohydrocracking herein will typically boil at a temperature above 150° C.The feedstocks can contain a substantial amount of nitrogen, e.g. atleast 10 wppm nitrogen, and even greater than 500 wppm, in the form oforganic nitrogen compounds. The feeds can also have a significant sulfurcontent, ranging from about 0.1 wt. % to 3 wt. %, or higher. If desired,the feeds can be treated in a known or conventional manner to reduce thesulfur and/or nitrogen content thereof. Examples of hydrocarbonfeedstocks are those derived from at least one of thermal treatment,catalytic treatment, extraction, dewaxing or fractionation of apetroleum crude or fraction thereof, shale oil, tar sands or syntheticcrude. For purposes of the present disclosure where it is desirable toproduce a lube basestock the feed can be a wide variety ofwax-containing feedstocks including feeds derived from crude oils, shaleoils and tar sands as well as synthetic feeds such as those derived fromthe Fischer-Tropsch process. Typical wax-containing feedstocks for thepreparation of lubricating base oils have initial boiling points ofabout 315° C. or higher, and include feeds such as reduced crudes,hydrocrackates, raffinates, hydrotreated oils, atmospheric gas oils,vacuum gas oils, coker gas oils, atmospheric and vacuum resids,deasphalted oils, slack waxes and Fischer-Tropsch wax. Such feeds may bederived from distillation towers (atmospheric and vacuum),hydrocrackers, hydrotreaters and solvent extraction units, and may havewax contents of up to 50% or more.

As an example, a feedstock can be subjected to hydrocracking in a firstzone in the presence of the catalyst derived from a suitable precursor.Hydrocracking conditions include temperatures of from 300 to 480° C.,hydrogen pressures of from 1000 to 3500 psig (6995 to 24234 KPa), liquidhourly space velocities of from 0.2 to 4.0 and hydrogen treat gas ratesof from 1000 to 15000 scf/B (178 to 2670 m³/m³). The product from thefirst hydrocracking zone may be fractionated to isolate a lubricatingoil fraction.

The product, i.e., hydrocrackate, from the first hydrocracking zone maybe further hydrocracked in a second hydrocracking zone. Thehydrocracking conditions in the second hydrocracking zone are the sameas those in the first hydrocracking zone. The hydrocracking catalyst inthe second hydrocracking zone may be the catalyst derived from asuitable precursor of the first hydrocracking zone, crystalline oramorphous metal oxides or mixtures thereof. Preferred crystalline metaloxides are molecular sieves including zeolites andsilicoaluminophosphates. Preferred zeolites include zeolite X and Ywhich may be supported on a refractory metal oxide. Preferred amorphousmetal oxides include silica-alumina.

The hydrocrackate from either the first or second hydrocracking zonesmay be further processed by fractionation to obtain a distillatelubricating oil fraction. This distillate fraction may then be solventextracted with conventional solvents such as furfural, phenol orN-methyl-2-pyrrolidone (NMP) under solvent extraction conditions.Raffinate from solvent extraction may then be further processed by acombination of dewaxing and/or hydrofinishing. Dewaxing may be bysolvent or catalytic dewaxing. Preferred solvent dewaxing utilizesconventional solvents including ketones such as methyl ethyl ketone,methyl isobutyl ketone or mixtures thereof. Catalytic dewaxing is by 8,10 or 12 ring molecular sieves, preferably 10 ring molecular sievesunder catalytic dewaxing conditions. Preferred 10 ring molecular sievesare zeolites or SAPOs. Preferred zeolites include ZSM-5, ZSM-22, ZSM-23,ZSM-35, ZSM-48 and ZSM-57. Preferred SAPOs include SAPO-11 and SAPO-41.In the alternative, the distillate fraction may be catalytically dewaxedwithout an intervening solvent extraction step.

The solvent or catalytically dewaxed product may then be hydrofinishedin a hydrofinishing zone under hydrofinishing conditions. Hydrofinishingconditions include a temperature of from 200° C. to 370° C., pressure offrom 150 to 3000 psig (1136 to 20786 kPa), liquid hourly space velocityof from 0.2 to 5.0 hr⁻¹, and a hydrogen treat rate of from 100 to 5000scf/B (17.8 to 890 m³/m³). Hydrofinishing catalysts may be the bulkmetal catalyst used in the hydrocracking zone or may be conventionalhydrofinishing catalysts such as those containing at least one GroupVIII metal on a refractory metal oxide support which may be promoted.The Group VIII metal may be combined with a Group VIB metal. If theGroup VIII metal is a non-noble metal, it is preferably combined with aGroup VIB metal.

Products from a process according to this type of aspect can includeGroup II and Group III lubricating oil basestocks. Group II basestockshave a saturates content of at least 90%, a sulfur content less than0.03 wt. % and a VI less than 120. Group III basestocks have a saturatescontent of at least 90%, a sulfur content less than 0.03 wt. % and a VIgreater than 120.

Multimetallic Catalyst and Forming Multimetallic Catalyst from aPrecursor

As used herein, the term “bulk”, when describing a mixed metal oxidecatalyst composition, indicates that the catalyst composition isself-supporting in that it does not require a carrier or support. It iswell understood that bulk catalysts may have some minor amount ofcarrier or support material in their compositions (e.g., about 20 wt %or less, about 15 wt % or less, about 10 wt % or less, about 5 wt % orless, or substantially no carrier or support, based on the total weightof the catalyst composition); for instance, bulk hydroprocessingcatalysts may contain a minor amount of a binder, e.g., to improve thephysical and/or thermal properties of the catalyst. In contrast,heterogeneous or supported catalyst systems typically comprise a carrieror support onto which one or more catalytically active materials aredeposited, often using an impregnation or coating technique.Nevertheless, heterogeneous catalyst systems without a carrier orsupport (or with a minor amount of carrier or support) are generallyreferred to as bulk catalysts and are frequently formed byco-precipitation or solid-solid reactions in slurries.

In some aspects, the methods described herein can include use of acatalyst formed from a catalyst precursor composition comprising atleast one metal from Group 6 of the Periodic Table of the Elements, atleast one metal from Groups 8-10 of the Periodic Table of the Elements,and a reaction product formed from (i) a first organic compoundcontaining at least one amine group and at least 10 carbons or (ii) asecond organic compound containing at least one carboxylic acid groupand at least 10 carbons, but not both (i) and (ii), wherein the reactionproduct contains additional unsaturated carbon atoms, relative to (i)the first organic compound or (ii) the second organic compound, whereinthe metals of the catalyst precursor composition are arranged in acrystal lattice, and wherein the reaction product is not located withinthe crystal lattice. This catalyst precursor composition can be a bulkmetal catalyst precursor composition or a supported metal catalystprecursor composition. When it is a bulk mixed metal catalyst precursorcomposition, the reaction product can be obtained by heating thecomposition (though specifically the amine-containing compound or thecarboxylic acid-containing compound) to a temperature from about 195° C.to about 260° C. for a time sufficient for the first or second organiccompounds to react to form additional in situ unsaturated carbon atomsand/or become more oxidized than the first or second organic compounds,but not for so long that more than 50% by weight of the first or secondorganic compound is volatilized, thereby forming a catalyst precursorcomposition that contains in situ formed unsaturated carbon atoms and/orthat is further oxidized.

Other aspects can relate to using a catalyst formed from a catalystprecursor composition containing in situ formed unsaturated carbonatoms. The catalyst can be formed from the precursor by a processcomprising: (a) treating a catalyst precursor composition comprising atleast one metal from Group 6 of the Periodic Table of the Elements, atleast one metal from Groups 8-10 of the Periodic Table of the Elements,with a first organic compound containing at least one amine group and atleast 10 carbon atoms or a second organic compound containing at leastone carboxylic acid group and at least 10 carbon atoms, to form anorganically treated precursor catalyst composition; and (b) heating saidorganically treated precursor catalyst composition at a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first orsecond organic compounds to react to form additional in situ unsaturatedcarbon atoms and/or become more oxidized, but not for so long that morethan 50% by weight of the first or second organic compound isvolatilized, thereby forming a catalyst precursor composition thatcontains in situ formed unsaturated carbon atoms and/or that is furtheroxidized. This process can be used to make a bulk metal catalystprecursor composition or a supported metal catalyst precursorcomposition. When used to make a bulk mixed metal catalyst precursorcomposition, the catalyst precursor composition containing in situformed unsaturated carbon atoms can, in one embodiment, consistessentially of the reaction product, an oxide form of the at least onemetal from Group 6, an oxide form of the at least one metal from Groups8-10, and optionally about 20 wt % or less of a binder.

As an example, when the catalyst precursor is a bulk mixed metalcatalyst precursor composition, the reaction product can be obtained byheating the composition (though specifically the first or second organiccompounds, or the amine-containing or carboxylic acid-containingcompound) to a temperature from about 195° C. to about 260° C. for atime sufficient to effectuate a dehydrogenation, and/or an at leastpartial decomposition, of the first or second organic compound to forman additional unsaturation and/or additional oxidation in the reactionproduct in situ. Accordingly, a bulk mixed metal hydroprocessingcatalyst composition can be produced from this bulk mixed metal catalystprecursor composition by sulfiding it under sufficient sulfidingconditions, which sulfiding should begin in the presence of the in situadditionally unsaturated reaction product (which may result from atleast partial decomposition, e.g., via oxidative dehydrogenation in thepresence of oxygen and/or via non-oxidative dehydrogenation in theabsence of an appropriate concentration of oxygen, oftypically-unfunctionalized organic portions of the first or secondorganic compounds, e.g., of an aliphatic portion of an organic compoundand/or through conjugation/aromatization of unsaturations expanding uponan unsaturated portion of an organic compound).

In still other aspects, a feed can be processed in a reaction systemthat includes a catalyst formed from a catalyst precursor compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a reaction product formed from (i) a first organiccompound containing at least one amine group, and (ii) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group. When this reaction product is an amide,the presence of the reaction product in any intermediate or finalcomposition can be determined by methods well known in the art, e.g., byinfrared spectroscopy (FTIR) techniques. When this reaction productcontains additional unsaturation(s) not present in the first and secondorganic compounds, e.g., from at least partialdecomposition/dehydrogenation at conditions including elevatedtemperatures, the presence of the additional unsaturation(s) in anyintermediate or final composition can be determined by methods wellknown in the art, e.g., by FTIR and/or nuclear magnetic resonance (¹³CNMR) techniques. This catalyst precursor composition can be a bulk metalcatalyst precursor composition or a heterogeneous (supported) metalcatalyst precursor composition.

More broadly, this type of aspect relates to use of a catalyst formedfrom a catalyst precursor composition comprising at least one metal fromGroup 6 of the Periodic Table of the Elements, at least one metal fromGroups 8-10 of the Periodic Table of the Elements, and a condensationreaction product formed from (i) a first organic compound containing atleast one first functional group, and (ii) a second organic compoundseparate from said first organic compound and containing at least onesecond functional group, wherein said first functional group and saidsecond functional group are capable of undergoing a condensationreaction and/or a (decomposition) reaction causing an additionalunsaturation to form an associated product. Though the description aboveand herein often refers specifically to the condensation reactionproduct being an amide, it should be understood that any in situcondensation reaction product formed can be substituted for the amidedescribed herein. For example, if the first functional group is ahydroxyl group and the second functional group is a carboxylic acid oran acid chloride or an organic ester capable of undergoingtransesterification with the hydroxyl group, then the in situcondensation reaction product formed would be an ester.

As an example, when the catalyst precursor is a bulk mixed metalcatalyst precursor composition, the reaction product can be obtained byheating the composition (such as the condensation reactants, or theamine-containing compound and/or the carboxylic acid-containingcompound) to a temperature from about 195° C. to about 260° C. for atime sufficient for the first and second organic compounds to form acondensation product, such as an amide, and/or an additional(decomposition) unsaturation in situ. Accordingly, a bulk mixed metalhydroprocessing catalyst composition can be produced from this bulkmixed metal catalyst precursor composition by sulfiding it undersufficient sulfiding conditions, which sulfiding should begin in thepresence of the in situ product, e.g., the amide (i.e., when present,the condensation product moiety, or amide, can be substantially presentand/or can preferably not be significantly decomposed by the beginningof the sulfiding step), and/or containing additional unsaturations(which may result from at least partial decomposition, e.g., viaoxidative dehydrogenation in the presence of oxygen and/or vianon-oxidative dehydrogenation in the absence of an appropriateconcentration of oxygen, of typically-unfunctionalized organic portionsof the first and/or second organic compounds, e.g., of an aliphaticportion of an organic compound and/or through conjugation/aromatizationof unsaturations expanding upon an unsaturated portion of an organiccompound or stemming from an interaction of the first and second organiccompounds at a site other than their respective functional groups).

In yet other aspects, a feed can be processed using a catalyst formedfrom a catalyst precursor composition containing an ex-situ formedreaction product. The catalyst can be formed from the precursor by aprocess comprising: (a) treating a catalyst precursor compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, with an amide-containing reaction product formed from afirst organic compound containing at least one amine group and at least10 carbon atoms or a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, to form anorganically treated precursor catalyst composition; and (b) heating saidorganically treated precursor catalyst composition at a temperature fromabout 195° C. to about 260° C. for a time sufficient for theamide-containing reaction product to form additional in situ unsaturatedcarbon atoms and/or become more oxidized, but not for so long that morethan 50% by weight of the first or second organic compound isvolatilized, thereby forming a catalyst precursor composition thatcontains in situ formed unsaturated carbon atoms and/or that is furtheroxidized. This process can be used to make a bulk metal catalystprecursor composition or a supported metal catalyst precursorcomposition. When used to make a bulk mixed metal catalyst precursorcomposition, the catalyst precursor composition can, in one embodiment,consist essentially of the reaction product containing furtherunsaturated carbon atoms and/or further oxidation, an oxide form of theat least one metal from Group 6, an oxide form of the at least one metalfrom Groups 8-10, and optionally about 20 wt or less of a binder.

When the catalyst precursor is a bulk mixed metal catalyst precursorcomposition, the thermal treatment of the amide-impregnated metal oxidecomponent is carried out by heating the impregnated composition to atemperature and for a time which does not result in gross decompositionof the amide, although additional unsaturation may arise from partial insitu decomposition; the temperature is typically from about 195° C. toabout 250° C. (or optionally about 195° C. to about 260° C.), but highertemperatures, e.g. in the range of 250 to 280° C., can be used in orderto abbreviate the duration of the heating although due care is requiredto avoid the gross decomposition of the pre-formed amide, as discussedfurther below. The bulk mixed metal hydroprocessing catalyst can beproduced from this precursor by sulfiding it with the sulfiding takingplace with the amide present on the metal oxide component (i.e., whenthe thermally treated amide, is substantially present and/or preferablynot significantly decomposed by the beginning of the sulfiding step).Additional unsaturation may be present in the organic component of thecatalyst precursor resulting from a variety of mechanisms includingpartial decomposition, (e.g., via oxidative dehydrogenation in thepresence of oxygen and/or via non-oxidative dehydrogenation in theabsence of an appropriate concentration of oxygen), oftypically-unfunctionalized organic portions of the amide and/or throughconjugation/aromatization of unsaturations expanding upon an unsaturatedportion the amide. The treated organic component may also containadditional oxygen in addition to the unsaturation when the treatment iscarried out in an oxidizing atmosphere.

Catalyst precursor compositions and hydroprocessing catalystcompositions useful in various aspects of the present disclosure canadvantageously comprise (or can have metal components that consistessentially of) at least one metal from Group 6 of the Periodic Table ofElements and at least one metal from Groups 8-10 of the Periodic Tableof Elements, and optionally at least one metal from Group 5 of thePeriodic Table of Elements. Generally, these metals are present in theirsubstantially fully oxidized form, which can typically take the form ofsimple metal oxides, but which may be present in a variety of otheroxide forms, e.g., such as hydroxides, oxyhydroxides, oxycarbonates,carbonates, oxynitrates, oxysulfates, or the like, or some combinationthereof. In one preferred embodiment, the Group 6 metal(s) can be Moand/or W, and the Group 8-10 metal(s) can be Co and/or Ni. Generally,the atomic ratio of the Group 6 metal(s) to the metal(s) of Groups 8-10can be from about 2:1 to about 1:3, for example from about 5:4 to about1:2, from about 5:4 to about 2:3, from about 5:4 to about 3:4, fromabout 10:9 to about 1:2, from about 10:9 to about 2:3, from about 10:9to about 3:4, from about 20:19 to about 2:3, or from about 20:19 toabout 3:4. When the composition further comprises at least one metalfrom Group 5, that at least one metal can be V and/or Nb. When present,the amount of Group 5 metal(s) can be such that the atomic ratio of theGroup 6 metal(s) to the Group 5 metal(s) can be from about 99:1 to about1:1, for example from about 99:1 to about 5:1, from about 99:1 to about10:1, or from about 99:1 to about 20:1. Additionally or alternately,when Group 5 metal(s) is(are) present, the atomic ratio of the sum ofthe Group 5 metal(s) plus the Group (6) metal(s) compared to themetal(s) of Groups 8-10 can be from about 2:1 to about 1:3, for examplefrom about 5:4 to about 1:2, from about 5:4 to about 2:3, from about 5:4to about 3:4, from about 10:9 to about 1:2, from about 10:9 to about2:3, from about 10:9 to about 3:4, from about 20:19 to about 2:3, orfrom about 20:19 to about 3:4.

The metals in the catalyst precursor compositions and in thehydroprocessing catalyst compositions according to the disclosure can bepresent in any suitable form prior to sulfiding, but can often beprovided as metal oxides. When provided as bulk mixed metal oxides, suchbulk oxide components of the catalyst precursor compositions and of thehydroprocessing catalyst compositions according to the disclosure can beprepared by any suitable method known in the art, but can generally beproduced by forming a slurry, typically an aqueous slurry, comprising(1) (a) an oxyanion of the Group 6 metal(s), such as a tungstate and/ora molybdate, or (b) an insoluble (oxide, acid) form of the Group 6metal(s), such as tungstic acid and/or molybdenum trioxide, (2) a saltof the Group 8-10 metal(s), such as nickel carbonate, and optionally,when present, (3) (a) a salt or oxyanion of a Group 5 metal, such as avanadate and/or a niobate, or (b) insoluble (oxide, acid) form of aGroup 5 metal, such as niobic acid and/or diniobium pentoxide. Theslurry can be heated to a suitable temperature, such as from about 60°C. to about 150° C., at a suitable pressure, e.g., at atmospheric orautogenous pressure, for an appropriate time, e.g., about 4 hours toabout 24 hours.

Non-limiting examples of suitable mixed metal oxide compositions caninclude, but are not limited to, nickel-tungsten oxides, cobalt-tungstenoxides, nickel-molybdenum oxides, cobalt-molybdenum oxides,nickel-molybdenum-tungsten oxides, cobalt-molybdenum-tungsten oxides,cobalt-nickel-tungsten oxides, cobalt-nickel-molybdenum oxides,cobalt-nickel-tungsten-molybdenum oxides, nickel-tungsten-niobiumoxides, nickel-tungsten-vanadium oxides, cobalt-tungsten-vanadiumoxides, cobalt-tungsten-niobium oxides, nickel-molybdenum-niobiumoxides, nickel-molybdenum-vanadium oxides,nickel-molybdenum-tungsten-niobium oxides,nickel-molybdenum-tungsten-vanadium oxides, and the like, andcombinations thereof.

Suitable mixed metal oxide compositions can advantageously exhibit aspecific surface area (as measured via the nitrogen BET method using aQuantachrome Autosorb™ apparatus) of at least about 20 m²/g, for exampleat least about 30 m²/g, at least about 40 m²/g, at least about 50 m²/g,at least about 60 m²/g, at least about 70 m²/g, or at least about 80m²/g. Additionally or alternately, the mixed metal oxide compositionscan exhibit a specific surface area of not more than about 500 m²/g, forexample not more than about 400 m²/g, not more than about 300 m²/g, notmore than about 250 m²/g, not more than about 200 m²/g, not more thanabout 175 m²/g, not more than about 150 m²/g, not more than about 125m²/g, or not more than about 100 m²/g.

In some aspects, after separating and drying the mixed metal oxide(slurry) composition, it can be treated, generally by impregnation, with(i) an effective amount of a first organic compound containing at leastone amine group or (ii) an effective amount of a second organic compoundseparate from the first organic compound and containing at least onecarboxylic acid group, but not both (i) and (ii).

In other aspects, after separating and drying the mixed metal oxide(slurry) composition, it can be treated, generally by impregnation, with(i) an effective amount of a first organic compound containing at leastone amine group, and (ii) an effective amount of a second organiccompound separate from the first organic compound and containing atleast one carboxylic acid group.

In still other aspects, after separating and drying the mixed metaloxide (slurry) composition, it can be treated, generally byimpregnation, with the pre-formed amide derived from (i) an effectiveamount of a first organic compound containing at least one amine group,and (ii) an effective amount of a second organic compound separate fromthe first organic compound and containing at least one carboxylic acidgroup. The amide is formed by a condensation reaction between the aminereactant and the carboxylic acid reactant; this reaction, carried out exsitu, is usually accomplished at mildly elevated temperatures.

In aspects where either a first or second organic compound is used, thefirst organic compound can comprise at least 10 carbon atoms, forexample can comprise from 10 to 20 carbon atoms or can comprise aprimary monoamine having from 10 to 30 carbon atoms. Additionally oralternately, the second organic compound can comprise at least 10 carbonatoms, for example can comprise from 10 to 20 carbon atoms or cancomprise only one carboxylic acid group and can have from 10 to 30carbon atoms.

In other aspects where both a first and second organic compound are used(including aspects where a first and second organic compound are reactedex situ to form an amide), the first organic compound can comprise atleast 10 carbon atoms, for example can comprise from 10 to 20 carbonatoms or can comprise a primary monoamine having from 10 to 30 carbonatoms. Additionally or alternately, the second organic compound cancomprise at least 10 carbon atoms, for example can comprise from 10 to20 carbon atoms or can comprise only one carboxylic acid group and canhave from 10 to 30 carbon atoms. Further additionally or alternately,the total number of carbon atoms comprised among both the first andsecond organic compounds can be at least 15 carbon atoms, for example atleast 20 carbon atoms, at least 25 carbon atoms, at least 30 carbonatoms, or at least 35 carbon atoms. Although in such embodiments theremay be no practical upper limit on total carbon atoms from both organiccompounds, in some embodiments, the total number of carbon atomscomprised among both the first and second organic compounds can be 100carbon atoms or less, for example 80 carbon atoms or less, 70 carbonatoms or less, 60 carbon atoms or less, or 50 carbon atoms or less.

Representative examples of organic compounds containing amine groups caninclude, but are not limited to, primary and/or secondary, linear,branched, and/or cyclic amines, such as triacontanylamine,octacosanylamine, hexacosanylamine, tetracosanylamine, docosanylamine,erucylamine, eicosanylamine, octadecylamine, oleylamine, linoleylamine,hexadecylamine, sapienylamine, palmitoleylamine, tetradecylamine,myristoleylamine, dodecylamine, decylamine, nonylamine, cyclooctylamine,octylamine, cycloheptylamine, heptylamine, cyclohexylamine,n-hexylamine, isopentylamine, n-pentylamine, t-butylamine, n-butylamine,isopropylamine, n-propylamine, adamantanamine, adamantanemethylamine,pyrrolidine, piperidine, piperazine, imidazole, pyrazole, pyrrole,pyrrolidine, pyrroline, indazole, indole, carbazole, norbomylamine,aniline, pyridylamine, benzylamine, aminotoluene, alanine, arginine,aspartic acid, glutamic acid, glutamine, glycine, histidine, isoleucine,leucine, lysine, phenylalanine, serine, threonine, valine,1-amino-2-propanol, 2-amino-1-propanol, diaminoeicosane,diaminooctadecane, diaminohexadecane, diaminotetradecane,diaminododecane, diaminodecane, 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, ethylenediamine,ethanolamine, p-phenylenediamine, o-phenylenediamine,m-phenylenediamine, 1,2-propylenediamine, 1,3-propylenediamine,1,4-diaminobutane, 1,3diamino-2-propanol, and the like, and combinationsthereof. In an embodiment, the molar ratio of the Group 6 metal(s) inthe composition to the first organic compound during treatment can befrom about 1:1 to about 20:1.

Additionally or alternately, in some aspects the amine portion of thefirst organic compound can be a part of a larger functional group inthat compound, so long as the amine portion (notably the amine nitrogenand the constituents attached thereto) retains its operability as aLewis base. For instance, the first organic compound can comprise aurea, which functional group comprises an amine portion attached to thecarbonyl portion of an amide group. In such an instance, the urea can beconsidered functionally as an “amine-containing” functional group forthe purposes of the present disclosure herein, except in situationswhere such inclusion is specifically contradicted. Aside from ureas,other examples of such amine-containing functional groups that may besuitable for satisfying the at least one amine group in the firstorganic compound can generally include, but are not limited to,hydrazides, sulfonamides, and the like, and combinations thereof.

The amine functional group from the first organic compound can includeprimary or secondary amines, as mentioned above, but generally does notinclude quaternary amines, and in some instances does not includetertiary amines either. Furthermore, the first organic compound canoptionally contain other functional groups besides amines. For instance,the first organic compound can comprise an aminoacid, which possesses anamine functional group and a carboxylic acid functional groupsimultaneously. Aside from carboxylic acids, other examples of suchsecondary functional groups in amine-containing organic compounds cangenerally include, but are not limited to, hydroxyls, aldehydes,anhydrides, ethers, esters, imines, imides, ketones, thiols(mercaptans), thioesters, and the like, and combinations thereof.

Additionally or alternately, in other aspects involving formation of acondensation product (including aspects involving ex situ formation ofan amide), the amine functional group from the first organic compoundcan include primary or secondary amines, as mentioned above, butgenerally does not include tertiary or quaternary amines, as tertiaryand quaternary amines tend not to be able to form amides. Furthermore,the first organic compound can contain other functional groups besidesamines, whether or not they are capable of participating in forming anamide or other condensation reaction product with one or more of thefunctional groups from second organic compound. For instance, the firstorganic compound can comprise an aminoacid, which possesses an aminefunctional group and a carboxylic acid functional group simultaneously.In such an instance, the aminoacid would qualify as only one of theorganic compounds, and not both; thus, in such an instance, either anadditional amine-containing (first) organic compound would need to bepresent (in the circumstance where the aminoacid would be considered thesecond organic compound) or an additional carboxylic acid-containing(second) organic compound would need to be present (in the circumstancewhere the aminoacid would be considered the first organic compound).Aside from carboxylic acids, other examples of such secondary functionalgroups in amine-containing organic compounds can generally include, butare not limited to, hydroxyls, aldehydes, anhydrides, ethers, esters,imines, imides, ketones, thiols (mercaptans), thioesters, and the like,and combinations thereof.

Additionally or alternately, the amine portion of the first organiccompound can be a part of a larger functional group in that compound, solong as the amine portion (notably the amine nitrogen and theconstituents attached thereto) retains the capability of participatingin forming an amide or other condensation reaction product with one ormore of the functional groups from second organic compound. Forinstance, the first organic compound can comprise a urea, whichfunctional group comprises an amine portion attached to the carbonylportion of an amide group. In such an instance, provided the amineportion of the urea functional group of the first organic compound wouldstill be able to undergo a condensation reaction with the carboxylicacid functional group of the second organic compound, then the urea canbe considered functionally as an “amine-containing” functional group forthe purposes of the present disclosure herein, except in situationswhere such inclusion is specifically contradicted. Aside from ureas,other examples of such amine-containing functional groups that may besuitable for satisfying the at least one amine group in the firstorganic compound can generally include, but are not limited to,hydrazides, sulfonamides, and the like, and combinations thereof.

Representative examples of organic compounds containing carboxylic acidscan include, but are not limited to, primary and/or secondary, linear,branched, and/or cyclic amines, such as triacontanoic acid, octacosanoicacid, hexacosanoic acid, tetracosanoic acid, docosanoic acid, erucicacid, docosahexanoic acid, eicosanoic acid, eicosapentanoic acid,arachidonic acid, octadecanoic acid, oleic acid, elaidic acid,stearidonic acid, linoleic acid, alpha-linolenic acid, hexadecanoicacid, sapienic acid, palmitoleic acid, tetradecanoic acid, myristoleicacid, dodecanoic acid, decanoic acid, nonanoic acid, cyclooctanoic acid,octanoic acid, cycloheptanoic acid, heptanoic acid, cyclohexanoic acid,hexanoic acid, adamantanecarboxylic acid, norbomaneacetic acid, benzoicacid, salicylic acid, acetylsalicylic acid, citric acid, maleic acid,malonic acid, glutaric acid, lactic acid, oxalic acid, tartaric acid,cinnamic acid, vanillic acid, succinic acid, adipic acid, phthalic acid,isophthalic acid, terephthalic acid, ethylenediaminetetracarboxylicacids (such as EDTA), fumaric acid, alanine, arginine, aspartic acid,glutamic acid, glutamine, glycine, histidine, isoleucine, leucine,lysine, phenylalanine, serine, threonine, valine,1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, and the like, and combinationsthereof. In an embodiment, the molar ratio of the Group 6 metal(s) inthe composition to the second organic compound during treatment can befrom about 3:1 to about 20:1.

In some aspects, the second organic compound can optionally containother functional groups besides carboxylic acids. For instance, thesecond organic compound can comprise an aminoacid, which possesses acarboxylic acid functional group and an amine functional groupsimultaneously. Aside from amines, other examples of such secondaryfunctional groups in carboxylic acid-containing organic compounds cangenerally include, but are not limited to, hydroxyls, aldehydes,anhydrides, ethers, esters, imines, imides, ketones, thiols(mercaptans), thioesters, and the like, and combinations thereof. Insome embodiments, the second organic compound can contain no additionalamine or alcohol functional groups in addition to the carboxylic acidfunctional group(s).

Additionally or alternately, the reactive portion of the second organiccompound can be a part of a larger functional group in that compoundand/or can be a derivative of a carboxylic acid that behaves similarlyenough to a carboxylic acid, such that the reactive portion and/orderivative retains its operability as a Lewis acid. One example of acarboxylic acid derivative can include an alkyl carboxylate ester, wherethe alkyl group does not substantially hinder (over a reasonable timescale) the Lewis acid functionality of the carboxylate portion of thefunctional group.

In other aspects involving formation of a condensation product(including aspects involving ex situ formation of an amide), the secondorganic compound can contain other functional groups besides carboxylicacids, whether or not they are capable of participating in forming anamide or other condensation reaction product with one or more of thefunctional groups from first organic compound. For instance, the secondorganic compound can comprise an aminoacid, which possesses a carboxylicacid functional group and an amine functional group simultaneously. Insuch an instance, the aminoacid would qualify as only one of the organiccompounds, and not both; thus, in such an instance, either an additionalamine-containing (first) organic compound would need to be present (inthe circumstance where the aminoacid would be considered the secondorganic compound) or an additional carboxylic acid-containing (second)organic compound would need to be present (in the circumstance where theaminoacid would be considered the first organic compound). Aside fromamines, other examples of such secondary functional groups in carboxylicacid-containing organic compounds can generally include, but are notlimited to, hydroxyls, aldehydes, anhydrides, ethers, esters, imines,imides, ketones, thiols (mercaptans), thioesters, and the like, andcombinations thereof.

Additionally or alternately, the reactive portion of the second organiccompound can be a part of a larger functional group in that compoundand/or can be a derivative of a carboxylic acid that behaves similarlyenough to a carboxylic acid in the presence of the amine functionalgroup of the first organic compound, such that the reactive portionand/or derivative retains the capability of participating in forming anamide or other desired condensation reaction product with one or more ofthe functional groups from first organic compound. One example of acarboxylic acid derivative can include an alkyl carboxylate ester, wherethe alkyl group does not substantially hinder (over a reasonable timescale) the condensation reaction between the amine and the carboxylateportion of the ester to form an amide.

For aspects involving formation of a condensation product (includingaspects involving ex situ formation of an amide), while there is not astrict limit on the ratio between the first organic compound and thesecond organic compound, because the goal of the addition of the firstand second organic compounds is to attain a condensation reactionproduct, it may be desirable to have a ratio of the reactive functionalgroups within the first and second organic compounds, respectively, fromabout 1:4 to about 4:1, for example from about 1:3 to about 3:1 or fromabout 1:2 to about 2:1.

In certain aspects, the organic compound(s)/additive(s) and/or thereaction product(s) are not located/incorporated within the crystallattice of the mixed metal oxide precursor composition, e.g., insteadbeing located on the surface and/or within the pore volume of theprecursor composition and/or being associated with (bound to) one ormore metals or oxides of metals in a manner that does not significantlyaffect the crystalline lattice of the mixed metal oxide precursorcomposition, as observed through XRD and/or other crystallographicspectra. It is noted that, in these certain embodiments, a sulfidedversion of the mixed metal oxide precursor composition can still haveits sulfided form affected by the organic compound(s)/additive(s) and/orthe reaction product(s), even though the oxide lattice is notsignificantly affected.

In some aspects, one way to attain a catalyst precursor compositioncontaining a decomposition/dehydrogenation reaction product, such as onecontaining additional unsaturations, includes: (a) treating a catalystprecursor composition, which comprises at least one metal from Group 6of the Periodic Table of the Elements and at least one metal from Groups8-10 of the Periodic Table of the Elements, with a first organiccompound containing at least one amine group or a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group, but not both, to form an organicallytreated precursor catalyst composition; and (b) heating the organicallytreated precursor catalyst composition at a temperature sufficient andfor a time sufficient for the first or second organic compounds to reactto form an in situ product containing additional unsaturation (forexample, depending upon the nature of the first or second organiccompound, the temperature can be from about 195° C. to about 260° C.,such as from about 200° C. to about 250° C.), thereby forming theadditionally-unsaturated and/or additionally oxidized catalyst precursorcomposition.

In certain advantageous embodiments, the heating step (b) above can beconducted for a sufficiently long time so as to form additionalunsaturation(s), which may result from at least partial decomposition(e.g., oxidative and/or non-oxidative dehydrogenation and/oraromatization) of some (typically-unfunctionalized organic) portions ofthe first or second organic compounds, but generally not for so longthat the at least partial decomposition volatilizes more than 50% byweight of the first or second organic compounds. Without being bound bytheory, it is believed that additional unsaturation(s) formed in situand present at the point of sulfiding the catalyst precursor compositionto form a sulfided (hydroprocessing) catalyst composition can somehowassist in controlling one or more of the following: the size of sulfidedcrystallites; the coordination of one or more of the metals duringsulfidation, such that a higher proportion of the one or more types ofmetals are in appropriate sites for promoting desired hydroprocessingreactions (such as hydrotreating, hydrodenitrogenation,hydrodesulfurization, hydrodeoxygenation, hydrodemetallation,hydrocracking including selective hydrocracking, hydroisomerization,hydrodewaxing, and the like, and combinations thereof, and/or forreducing/minimizing undesired hydroprocessing reactions, such asaromatic saturation, hydrogenation of double bonds, and the like, andcombinations thereof) than for sulfided catalysts made in the absence ofthe in situ formed reaction product having additional unsaturation(s);and coordination/catalysis involving one or more of the metals aftersulfidation, such that a higher proportion (or each) of the one or moretypes of metals are more efficient at promoting desired hydroprocessingreactions (e.g., because the higher proportion of metal sites cancatalyze more hydrodesulfurization reactions of the same type in a giventimescale and/or because the higher proportion of the metal sites cancatalyze more difficult hydrodesulfurization reactions in a similartimescale) than for sulfided catalysts made in the absence of the insitu formed reaction product having additional unsaturation(s).

In other aspects, one way to attain a catalyst precursor compositioncontaining a condensation reaction product, such as an amide, and/or areaction product containing additional unsaturations includes: (a)treating a catalyst precursor composition, which comprises at least onemetal from Group 6 of the Periodic Table of the Elements and at leastone metal from Groups 8-10 of the Periodic Table of the Elements, with afirst organic compound containing at least one amine group and a secondorganic compound separate from said first organic compound andcontaining at least one carboxylic acid group to form an organicallytreated precursor catalyst composition; and (b) heating the organicallytreated precursor catalyst composition at a temperature sufficient andfor a time sufficient for the first and second organic compounds toreact to form an in situ condensation product and/or an in situ productcontaining additional unsaturation (for amides made from amines andcarboxylic acids, for example, the temperature can be from about 195° C.to about 260° C., such as from about 200° C. to about 250° C.), therebyforming the amide-containing and/or additionally-unsaturated and/oradditionally oxidized catalyst precursor composition.

Practically, the treating step (a) above can comprise one (or more) ofthree methods: (1) first treating the catalyst precursor compositionwith the first organic compound and second with the second organiccompound; (2) first treating the catalyst precursor composition with thesecond organic compound and second with the first organic compound;and/or (3) treating the catalyst precursor composition simultaneouslywith the first organic compound and with the second organic compound.

In certain advantageous embodiments, the heating step (b) above can beconducted for a sufficiently long time so as to form the amide, but notfor so long that the amide so formed substantially decomposes.Additionally or alternately in such advantageous embodiments, theheating step (b) above can be conducted for a sufficiently long time soas to form additional unsaturation(s), which may result from at leastpartial decomposition (e.g., oxidative and/or non-oxidativedehydrogenation and/or aromatization) of some(typically-unfunctionalized organic) portions of the organic compounds,but generally not for so long that the at least partial decomposition(i) substantially decomposes any condensation product, such as amide,and/or (ii) volatilizes more than 50% by weight of the combined firstand second organic compounds. Without being bound by theory, it isbelieved that in situ formed amide and/or additional unsaturation(s)present at the point of sulfiding the catalyst precursor composition toform a sulfided (hydroprocessing) catalyst composition can somehowassist in controlling one or more of the following: the size of sulfidedcrystallites; the coordination of one or more of the metals duringsulfidation, such that a higher proportion of the one or more types ofmetals are in appropriate sites for promoting desired hydroprocessingreactions (such as hydrotreating, hydrodenitrogenation,hydrodesulfurization, hydrodeoxygenation, hydrodemetallation,hydrocracking including selective hydrocracking, hydroisomerization,hydrodewaxing, and the like, and combinations thereof, and/or forreducing/minimizing undesired hydroprocessing reactions, such asaromatic saturation, hydrogenation of double bonds, and the like, andcombinations thereof) than for sulfided catalysts made in the absence ofthe in situ formed reaction product having an amide (condensationreaction product of functional groups) and/or additionalunsaturation(s); and coordination/catalysis involving one or more of themetals after sulfidation, such that a higher proportion (or each) of theone or more types of metals are more efficient at promoting desiredhydroprocessing reactions (e.g., because the higher proportion of metalsites can catalyze more hydrodesulfurization reactions of the same typein a given timescale and/or because the higher proportion of the metalsites can catalyze more difficult hydrodesulfurization reactions in asimilar timescale) than for sulfided catalysts made in the absence ofthe in situ formed reaction product having an amide (condensationreaction product of functional groups) and/or additionalunsaturation(s).

When used to make a bulk mixed metal catalyst precursor composition, thein situ reacted catalyst precursor composition can, in one embodiment,consist essentially of the reaction product, an oxide form of the atleast one metal from Group 6, an oxide form of the at least one metalfrom Groups 8-10, and optionally about 20 wt % or less of a binder(e.g., about 10 wt % or less).

After treatment of the catalyst precursor containing the at least oneGroup 6 metal and the at least one Group 8-10 metal with the firstand/or second organic compounds, the organically treated catalystprecursor composition can be heated to a temperature high enough to formthe reaction product and optionally but preferably high enough to enableany dehydrogenation/decomposition/condensation byproduct to be easilyremoved (e.g., in order to drive the reaction equilibrium to the atleast partially dehydrogenated/decomposed product and/or condensationproduct). Additionally or alternately, the organically treated catalystprecursor composition can be heated to a temperature low enough so as tosubstantially retain the reaction product containing the additionalunsaturations and/or the condensation product, so as not tosignificantly decompose the reaction product, and/or so as not tosignificantly volatilize (more than 50% by weight of) the first and/orsecond organic compounds (whether reacted or not).

It is contemplated that the specific lower and upper temperature limitsbased on the above considerations can be highly dependent upon a varietyof factors that can include, but are not limited to, the atmosphereunder which the heating is conducted, the chemical and/or physicalproperties of the first organic compound, the second organic compound,the reaction product, and/or any reaction byproduct, or a combinationthereof. In one embodiment, the heating temperature can be at leastabout 120° C., for example at least about 150° C., at least about 165°C., at least about 175° C., at least about 185° C., at least about 195°C., at least about 200° C., at least about 210° C., at least about 220°C., at least about 230° C., at least about 240° C., or at least about250° C. Additionally or alternately, the heating temperature can be notgreater than about 400° C., for example not greater than about 375° C.,not greater than about 350° C., not greater than about 325° C., notgreater than about 300° C., not greater than about 275° C., not greaterthan about 250° C., not greater than about 240° C., not greater thanabout 230° C., not greater than about 220° C., not greater than about210° C., or not greater than about 200° C.

In one embodiment, the heating can be conducted in a low- ornon-oxidizing atmosphere (and conveniently in an inert atmosphere, suchas nitrogen). In an alternate embodiment, the heating can be conductedin a moderately- or highly-oxidizing environment. In another alternateembodiment, the heating can include a multi-step process in which one ormore heating steps can be conducted in the low- or non-oxidizingatmosphere, in which one or more heating steps can be conducted in themoderately- or highly-oxidizing environment, or both. Of course, theperiod of time for the heating in the environment can be tailored to thefirst or second organic compound, but can typically extend from about 5minutes to about 168 hours, for example from about 10 minutes to about96 hours, from about 10 minutes to about 48 hours, from about 10 minutesto about 24 hours, from about 10 minutes to about 18 hours, from about10 minutes to about 12 hours, from about 10 minutes to about 8 hours,from about 10 minutes to about 6 hours, from about 10 minutes to about 4hours, from about 20 minutes to about 96 hours, from about 20 minutes toabout 48 hours, from about 20 minutes to about 24 hours, from about 20minutes to about 18 hours, from about 20 minutes to about 12 hours, fromabout 20 minutes to about 8 hours, from about 20 minutes to about 6hours, from about 20 minutes to about 4 hours, from about 30 minutes toabout 96 hours, from about 30 minutes to about 48 hours, from about 30minutes to about 24 hours, from about 30 minutes to about 18 hours, fromabout 30 minutes to about 12 hours, from about 30 minutes to about 8hours, from about 30 minutes to about 6 hours, from about 30 minutes toabout 4 hours, from about 45 minutes to about 96 hours, from about 45minutes to about 48 hours, from about 45 minutes to about 24 hours, fromabout 45 minutes to about 18 hours, from about 45 minutes to about 12hours, from about 45 minutes to about 8 hours, from about 45 minutes toabout 6 hours, from about 45 minutes to about 4 hours, from about 1 hourto about 96 hours, from about 1 hour to about 48 hours, from about 1hour to about 24 hours, from about 1 hour to about 18 hours, from about1 hour to about 12 hours, from about 1 hour to about 8 hours, from 1hour minutes to about 6 hours, or from about 1 hour to about 4 hours.

Additionally or alternately, in aspects where an ex situ formed amide isused, the amide can be formed prior to impregnation into the metal oxidecomponent of the catalyst precursor by reaction of the amine componentand the carboxylic acid component. Reaction typically takes placereadily at mildly elevated temperatures up to about 200° C. withliberation of water as a by-product of the reaction at temperaturesabove 100° C. and usually above 150° C. The reactants can usually beheated together to form a melt in which the reaction takes place and themelt impregnated directly into the metal oxide component which ispreferably pre-heated to the same temperature as the melt in order toassist penetration into the structure of the metal oxide component. Thereaction can also be carried out in the presence of a solvent if desiredand the resulting solution used for the impregnation step. In certainembodiments, the amide and its heat treated derivative may not belocated/incorporated within the crystal lattice of the mixed metal oxideprecursor, e.g., may instead be located on the surface and/or within thepore volume of the precursor and/or be associated with (bound to) one ormore metals or oxides of metals in a manner that does not significantlyaffect the crystalline lattice of the mixed metal oxide precursorcomposition, as observed through XRD and/or other crystallographicspectra. A sulfided version of the mixed metal oxide precursorcomposition can still have its sulfided form affected by the organiccompound(s)/additive(s) and/or the reaction product(s), even though theoxide lattice is not significantly affected.

There is not a strict limit on the ratio between the amine reactant andthe carboxylic reactant, and accordingly, the ratio of the reactiveamine and carboxylic acid groups in the two reactants may vary,respectively, from about 1:4 to about 4:1, for example from about 1:3 toabout 3:1 or from about 1:2 to about 2:1. It has been observed thatcatalysts made with amides from equimolar quantities of the amine andcarboxylic acid reactants compounds show performance improvements inhydroprocessing certain feeds and for this reason, amides made with anequimolar ratio are preferred.

The pre-formed amide is suitably impregnated into the metal oxideprecursor by incipient wetness impregnation with the amount determinedaccording to the pore volume of the metal oxide component. Followingimpregnation, a heat treatment is carried out which first removes anyresidual water and/or solvent but also creates a reaction productcontaining additional unsaturation sites and possibly additional oxygen.The amide-impregnated metal oxide component is then heated at atemperature sufficient and for a time sufficient to form a productcontaining the additional unsaturation which is characteristic of thedesired organic component; this treatment with the pre-formed amide istypically from about 195° C. to about 280° C., for example from about200° C. to about 250° C.).

The heating step should not be conducted for so long that the amidebecomes substantially decomposed but is continued for a sufficientlylong time to form additional unsaturation(s), which may result from atleast partial decomposition (e.g., oxidative and/or non-oxidativedehydrogenation and/or aromatization) of some(typically-unfunctionalized organic) portions of the organic compounds.On the other hand, the heating should not be conducted for so long thatthe decomposition substantially results in gross decomposition of theamide or any condensation product. The impregnated catalyst precursorcomposition can be heated to a temperature high enough to form theunsaturated reaction product and typically high enough to enable anybyproducts such as water to be removed. The temperature to which theimpregnated precursor composition is heated should, however, maintainedlow enough so as to substantially retain the amide reaction product withthe additional unsaturations and any oxygen, and so as not tosignificantly decompose the functionalized reaction product, and/or soas not to significantly volatilize (more than 50% by weight of) theamide.

The specific lower and upper temperature limits based on the aboveconsiderations can be dependent upon a variety of factors that caninclude, but are not limited to, the atmosphere under which the heatingis conducted, the chemical and/or physical properties of the amide, theamide reaction product, and/or any functionalized reaction byproduct aswell as the desired duration of the heating with higher temperatures,e.g. over the optimal temperature range up to 250° C., enabling shorterheating durations to be utilized. The minimum heating temperature can,for example, suitably be at least about 120° C., for example at leastabout 150° C., at least about 165° C., at least about 175° C., at leastabout 185° C., at least about 195° C., at least about 200° C., at leastabout 210° C., at least about 220° C., at least about 230° C., at leastabout 240° C., or at least about 250° C. The maximum heating temperatureshould not be greater than about 400° C., for example, not greater thanabout 375° C., not greater than about 350° C., not greater than about325° C., not greater than about 300° C., not greater than about 275° C.,not greater than about 250° C., not greater than about 240° C., notgreater than about 230° C., not greater than about 220° C., not greaterthan about 210° C., or not greater than about 200° C. Resort totemperatures above the preferred maximum of 250° C. should be made withdue care to avoid the gross decomposition of the amide as noted abovebut a slightly higher range, for example, 250-280° C., e.g. 260 or 275°C. may permit usefully shorter heating steps in commercial scaleoperation. The temperature to be used should therefore be selected on anempirical basis depending on the nature of the amide used in theimpregnation. The progress of the heating can be monitored according tothe properties of the treated product, including analysis by GC-MS andby its infrared spectrum as described below.

In an embodiment, the organically treated catalyst precursor compositionand/or the catalyst precursor composition containing the reactionproduct can contain from about 4 wt % to about 20 wt %, for example fromabout 5 wt % to about 15 wt %, carbon resulting from the first andsecond organic compounds and/or from the condensation product, asapplicable, based on the total weight of the relevant composition.

Additionally or alternately, as a result of the heating step, thereaction product from the organically treated catalyst precursor canexhibit a content of unsaturated carbon atoms (which includes aromaticcarbon atoms), as measured according to peak area comparisons using ¹³CNMR techniques, of at least 29%, for example at least about 30%, atleast about 31%, at least about 32%, or at least about 33%. Furtheradditionally or alternately, the reaction product from the organicallytreated catalyst precursor can optionally exhibit a content ofunsaturated carbon atoms (which includes aromatic carbon atoms), asmeasured according to peak area comparisons using ¹³C NMR techniques, ofup to about 70%, for example up to about 65%, up to about 60%, up toabout 55%, up to about 50%, up to about 45%, up to about 40%, or up toabout 35%. Still further additionally or alternately, as a result of theheating step, the reaction product from the organically treated catalystprecursor can exhibit an increase in content of unsaturated carbon atoms(which includes aromatic carbon atoms), as measured according to peakarea comparisons using ¹³C NMR techniques, of at least about 17%, forexample at least about 18%, at least about 19%, at least about 20%, orat least about 21% (e.g., in an embodiment where the first organiccompound is oleylamine and the second organic compound is oleic acid,such that the combined unsaturation level of the unreacted compounds isabout 11.1% of carbon atoms, a about.17% increase in unsaturated carbonsupon heating corresponds to about 28.1% content of unsaturated carbonatoms in the reaction product). Yet further additionally or alternately,the reaction product from the organically treated catalyst precursor canoptionally exhibit an increase in content of unsaturated carbon atoms(which includes aromatic carbon atoms), as measured according to peakarea comparisons using ¹³C NMR techniques, of up to about 60%, forexample up to about 55%, up to about 50%, up to about 45%, up to about40%, up to about 35%, up to about 30%, or up to about 25%.

Again further additionally or alternately, as a result of the heatingstep, the reaction product from the organically treated catalystprecursor can exhibit a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹ (e.g., at about 1715 cm⁻¹), compared to adeconvoluted peak centered from about 1380 cm⁻¹ to about 1450 cm⁻¹(e.g., from about 1395 cm⁻¹ to about 1415 cm⁻¹), of at least 0.9, forexample at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least1.4, at least 1.5, at least 1.7, at least 2.0, at least 2.2, at least2.5, at least 2.7, or at least 3.0. Again still further additionally oralternately, the reaction product from the organically treated catalystprecursor can exhibit a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹ (e.g., at about 1715 cm⁻¹), compared to adeconvoluted peak centered from about 1380 cm⁻¹ to about 1450 cm⁻¹(e.g., from about 1395 cm⁻¹ to about 1415 cm⁻¹), of up to 15, forexample up to 10, up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.5,up to 4.0, up to 3.5, or up to 3.0.

A (sulfided) hydroprocessing catalyst composition can then be producedby sulfiding the catalyst precursor composition containing the reactionproduct. Sulfiding is generally carried out by contacting the catalystprecursor composition containing the reaction product with asulfur-containing compound (e.g., elemental sulfur, hydrogen sulfide,polysulfides, or the like, or a combination thereof, which may originatefrom a fossil/mineral oil stream, from a biocomponent-based oil stream,from a combination thereof, or from a sulfur-containing stream separatefrom the aforementioned oil stream(s)) at a temperature and for a timesufficient to substantially sulfide the composition and/or sufficient torender the sulfided composition active as a hydroprocessing catalyst.For instance, the sulfidation can be carried out at a temperature fromabout 300° C. to about 400° C., e.g., from about 310° C. to about 350°C., for a period of time from about 30 minutes to about 96 hours, e.g.,from about 1 hour to about 48 hours or from about 4 hours to about 24hours. The sulfiding can generally be conducted before or aftercombining the metal (oxide) containing composition with a binder, ifdesired, and before or after forming the composition into a shapedcatalyst. The sulfiding can additionally or alternately be conducted insitu in a hydroprocessing reactor. Obviously, to the extent that areaction product of the first or second organic compounds containsadditional unsaturations formed in situ, it would generally be desirablefor the sulfidation (and/or any catalyst treatment after the organictreatment) to significantly maintain the in situ formed additionalunsaturations of said reaction product.

The sulfided catalyst composition can exhibit a layered structurecomprising a plurality of stacked YS₂ layers, where Y is the Group 6metal(s), such that the average number of stacks (typically for bulkorganically treated catalysts) can be from about 1.5 to about 3.5, forexample from about 1.5 to about 3.0, from about 2.0 to about 3.3, fromabout 2.0 to about 3.0, or from about 2.1 to about 2.8. For instance,the treatment of the metal (oxide) containing precursor compositionaccording to the disclosure can afford a decrease in the average numberof stacks of the treated precursor of at least about 0.8, for example atleast about 1.0, at least about 1.2, at least about 1.3, at least about1.4, or at least about 1.5, as compared to an untreated metal (oxide)containing precursor composition. As such, the number of stacks can beconsiderably less than that obtained with an equivalent sulfided mixedmetal (oxide) containing precursor composition produced without thefirst or second organic compound treatment. The reduction in the averagenumber of stacks can be evidenced, e.g., via X-ray diffraction spectraof relevant sulfided compositions, in which the (002) peak appearssignificantly broader (as determined by the same width at thehalf-height of the peak) than the corresponding peak in the spectrum ofthe sulfided mixed metal (oxide) containing precursor compositionproduced without the organic treatment (and/or, in certain cases, withonly a single organic compound treatment using an organic compoundhaving less than 10 carbon atoms) according to the present disclosure.Additionally or alternately to X-ray diffraction, transmission electronmicroscopy (TEM) can be used to obtain micrographs of relevant sulfidedcompositions, including multiple microcrystals, within which micrographimages the multiple microcrystals can be visually analyzed for thenumber of stacks in each, which can then be averaged over the micrographvisual field to obtain an average number of stacks that can evidence areduction in average number of stacks compared to a sulfided mixed metal(oxide) containing precursor composition produced without the organictreatment (and/or, in certain cases, with only a single organic compoundtreatment) according to the present disclosure.

The sulfided catalyst composition described above can be used as ahydroprocessing catalyst, either alone or in combination with a binder.If the sulfided catalyst composition is a bulk catalyst, then only arelatively small amount of binder may be added. However, if the sulfidedcatalyst composition is a heterogeneous/supported catalyst, then usuallythe binder is a significant portion of the catalyst composition, e.g.,at least about 40 wt %, at least about 50 wt %, at least about 60 wt %,or at least about 70 wt %; additionally or alternately forheterogeneous/supported catalysts, the binder can comprise up to about95 wt % of the catalyst composition, e.g., up to about 90 wt %, up toabout 85 wt %, up to about 80 wt %, up to about 75 wt %, or up to about70 wt %. Non-limiting examples of suitable binder materials can include,but are not limited to, silica, silica-alumina (e.g., conventionalsilica-alumina, silica-coated alumina, alumina-coated silica, or thelike, or a combination thereof), alumina (e.g., boehmite,pseudo-boehmite, gibbsite, or the like, or a combination thereof),titania, zirconia, cationic clays or anionic clays (e.g., saponite,bentonite, kaoline, sepiolite, hydrotalcite, or the like, or acombination thereof), and mixtures thereof. In some preferredembodiments, the binder can include silica, silica-alumina, alumina,titania, zirconia, and mixtures thereof. These binders may be applied assuch or after peptization. It may also be possible to apply precursorsof these binders that, during precursor synthesis, can be converted intoany of the above-described binders. Suitable precursors can include,e.g., alkali metal aluminates (alumina binder), water glass (silicabinder), a mixture of alkali metal aluminates and water glass(silica-alumina binder), a mixture of sources of a di-, tri-, and/ortetravalent metal, such as a mixture of water-soluble salts ofmagnesium, aluminum, and/or silicon (cationic clay and/or anionic clay),chlorohydrol, aluminum sulfate, or mixtures thereof.

Generally, the binder material to be used can have lower catalyticactivity than the remainder of the catalyst composition, or can havesubstantially no catalytic activity at all (less than about 5%, based onthe catalytic activity of the bulk catalyst composition being about100%). Consequently, by using a binder material, the activity of thecatalyst composition may be reduced. Therefore, the amount of bindermaterial to be used, at least in bulk catalysts, can generally depend onthe desired activity of the final catalyst composition. Binder amountsup to about 25 wt % of the total composition can be suitable (whenpresent, from above 0 wt % to about 25 wt %), depending on the envisagedcatalytic application. However, to take advantage of the resultingunusual high activity of bulk catalyst compositions according to thedisclosure, binder amounts, when added, can generally be from about 0.5wt % to about 20 wt % of the total catalyst composition.

If desired in bulk catalyst cases, the binder material can be compositedwith a source of a Group 6 metal and/or a source of a non-noble Group8-10 metal, prior to being composited with the bulk catalyst compositionand/or prior to being added during the preparation thereof. Compositingthe binder material with any of these metals may be carried out by anyknown means, e.g., impregnation of the (solid) binder material withthese metal(s) sources.

A cracking component may also be added during catalyst preparation. Whenused, the cracking component can represent from about 0.5 wt % to about30 wt %, based on the total weight of the catalyst composition. Thecracking component may serve, for example, as an isomerization enhancer.Conventional cracking components can be used, e.g., a cationic clay, ananionic clay, a zeolite (such as ZSM-5, zeolite Y, ultra-stable zeoliteY, zeolite X, an AlPO, a SAPO, or the like, or a combination thereof),amorphous cracking components (such as silica-alumina or the like), or acombination thereof. It is to be understood that some materials may actas a binder and a cracking component at the same time. For instance,silica-alumina may simultaneously have both a cracking and a bindingfunction.

If desired, the cracking component may be composited with a Group 6metal and/or a Group 8-10 non-noble metal, prior to being compositedwith the catalyst composition and/or prior to being added during thepreparation thereof. Compositing the cracking component with any ofthese metals may be carried out by any known means, e.g., impregnationof the cracking component with these metal(s) sources. When both acracking component and a binder material are used and when compositingof additional metal components is desired on both, the compositing maybe done on each component separately or may be accomplished by combiningthe components and doing a single compositing step.

The selection of particular cracking components, if any, can depend onthe intended catalytic application of the final catalyst composition.For instance, a zeolite can be added if the resulting composition is tobe applied in hydrocracking or fluid catalytic cracking. Other crackingcomponents, such as silica-alumina or cationic clays, can be added ifthe final catalyst composition is to be used in hydrotreatingapplications. The amount of added cracking material can depend on thedesired activity of the final composition and the intended application,and thus, when present, may vary from above 0 wt % to about 80 wt %,based on the total weight of the catalyst composition. In a preferredembodiment, the combination of cracking component and binder materialcan comprise less than 50 wt % of the catalyst composition, for example,less than about 40 wt %, less than about 30 wt %, less than about 20 wt%, less than about 15 wt %, or less than about 10 wt %.

If desired, further materials can be added, in addition to the metalcomponents already added, such as any material that would be addedduring conventional hydroprocessing catalyst preparation. Suitableexamples of such further materials can include, but are not limited to,phosphorus compounds, boron compounds, fluorine-containing compounds,sources of additional transition metals, sources of rare earth metals,fillers, or mixtures thereof.

ADDITIONAL EMBODIMENTS Embodiment 1

A process for selectively hydroconverting a raffinate produced fromsolvent refining a lubricating oil feedstock, comprising: conducting thelubricating oil feedstock to a solvent extraction zone and separatingtherefrom an aromatics rich extract and a paraffins rich raffinate;stripping the raffinate of solvent to produce a raffinate feed having adewaxed oil viscosity index from about 80 to about 105 and a finalboiling point of no greater than about 650° C.; passing the raffinatefeed to a first hydroconversion zone and processing the raffinate feedin the presence of a mixed metal catalyst under hydroconversionconditions; and passing the first hydroconverted raffinate to a secondreaction zone and conducting cold hydrofinishing of the firsthydroconverted raffinate in the presence of a hydrofinishing catalystunder cold hydrofinishing conditions, wherein the mixed metal catalystcomprises a sulfided mixed metal catalyst formed by sulfiding a mixedmetal catalyst precursor composition, the mixed metal catalyst precursorcomposition being produced by a) heating a composition comprising atleast one metal from Group 6 of the Periodic Table of the Elements, atleast one metal from Groups 8-10 of the Periodic Table of the Elements,and a reaction product formed from (i) a first organic compoundcontaining at least one amine group, and (ii) a second organic compoundseparate from said first organic compound and containing at least onecarboxylic acid group to a temperature from about 195° C. to about 260°C. for a time sufficient for the first and second organic compounds toform a reaction product in situ that contains an amide moiety,unsaturated carbon atoms not present in the first or second organiccompounds, or both; b) heating a composition comprising one metal fromGroup 6 of the Periodic Table of the Elements, at least one metal fromGroups 8-10 of the Periodic Table of the Elements, and a reactionproduct formed from (iii) a first organic compound containing at leastone amine group and at least 10 carbon atoms or (iv) a second organiccompound containing at least one carboxylic acid group and at least 10carbon atoms, but not both (iii) and (iv), wherein the reaction productcontains additional unsaturated carbon atoms, relative to (iii) thefirst organic compound or (iv) the second organic compound, wherein themetals of the catalyst precursor composition are arranged in a crystallattice, and wherein the reaction product is not located within thecrystal lattice, to a temperature from about 195° C. to about 260° C.for a time sufficient for the first or second organic compounds to forma reaction product in situ that contains unsaturated carbon atoms notpresent in the first or second organic compounds; or c) heating acomposition comprising at least one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a pre-formed amide formed from (v) afirst organic compound containing at least one amine group, and (vi) asecond organic compound separate from said first organic compound andcontaining at least one carboxylic acid group, to form additional insitu unsaturated carbon atoms not present in the first organic compound,the second organic compound, or both, but not for so long that thepre-formed amide substantially decomposes, thereby forming a catalystprecursor containing in situ formed unsaturated carbon atoms.

Embodiment 2

The process of Embodiment 1, further comprising passing the raffinatefeed into a second hydroconversion zone and processing the raffinatefeed in the presence of a hydroconversion catalyst under secondeffective hydroconversion conditions, the raffinate feed being passedinto the second hydroconversion zone prior to being passed into thefirst hydroconversion zone or after being passed into the firsthydroconversion zone.

Embodiment 3

The process of any of the above embodiments, wherein the hydroconversionconditions in the first hydroconversion zone, the second hydroconversionzone, or both the first and second hydroconversion zones includetemperatures of from 250° C. to 420° C., hydrogen pressures of from 300to 3000 psig (2170 to 20786 kPa), liquid hourly space velocities of from0.1 to 10 hr⁻¹, and hydrogen treat gas rates of from 500 to 5000 scf/B(89 to 890 m³/m³).

Embodiment 4

The process of any of the above embodiments, wherein the coldhydrofinishing conditions include temperatures of from 150° C. to 360°C., hydrogen pressures of from 300 to 3000 psig (2170 to 20786 kPa),liquid hourly space velocities of from 0.1 to 10 and hydrogen treat gasrates of from 500 to 5000 scf/B (89 to 890 m³/m³).

Embodiment 5

The process of any of the above embodiments, wherein solvent in thesolvent extraction zone is at least one of furfural, phenol orN-methyl-2-pyrrolidone.

Embodiment 6

The process of any of the above embodiments, wherein the coldhydrofinishing step is preceded by or followed by dewaxing, the dewaxingcomprising solvent dewaxing under solvent dewaxing conditions, catalyticdewaxing under catalytic dewaxing conditions, or a combination thereof.

Embodiment 7

A process for producing a lubricating oil feedstock, comprising:exposing a feedstock to a mixed metal catalyst under effectivehydroprocessing conditions to form a hydroprocessed effluent; separatingthe hydroprocessed effluent to form at least a gas phase effluent and aliquid hydroprocessed effluent; optionally exposing at least a portionof the liquid hydroprocessed effluent to a hydrocracking catalyst undereffective hydrocracking conditions to form a hydrocracked effluent;exposing at least a portion of the optionally hydrocracked effluent to adewaxing catalyst under effective catalytic dewaxing conditions to forman optionally hydrocracked, dewaxed effluent, wherein the mixed metalcatalyst comprises a sulfided mixed metal catalyst formed by sulfiding amixed metal catalyst precursor composition, the mixed metal catalystprecursor composition being produced by a) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a reaction product formed from (i) a first organiccompound containing at least one amine group, and (ii) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group to a temperature from about 195° C. toabout 250° C. for a time sufficient for the first and second organiccompounds to form a reaction product in situ that contains an amidemoiety, unsaturated carbon atoms not present in the first or secondorganic compounds, or both; b) heating a composition comprising onemetal from Group 6 of the Periodic Table of the Elements, at least onemetal from Groups 8-10 of the Periodic Table of the Elements, and areaction product formed from (iii) a first organic compound containingat least one amine group and at least 10 carbon atoms or (iv) a secondorganic compound containing at least one carboxylic acid group and atleast 10 carbon atoms, but not both (iii) and (iv), wherein the reactionproduct contains additional unsaturated carbon atoms, relative to (iii)the first organic compound or (iv) the second organic compound, whereinthe metals of the catalyst precursor composition are arranged in acrystal lattice, and wherein the reaction product is not located withinthe crystal lattice, to a temperature from about 195° C. to about 250°C. for a time sufficient for the first or second organic compounds toform a reaction product in situ that contains unsaturated carbon atomsnot present in the first or second organic compounds; or c) heating acomposition comprising at least one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a pre-formed amide formed from (v) afirst organic compound containing at least one amine group, and (vi) asecond organic compound separate from said first organic compound andcontaining at least one carboxylic acid group, to form additional insitu unsaturated carbon atoms not present in the first organic compound,the second organic compound, or both, but not for so long that thepre-formed amide substantially decomposes, thereby forming a catalystprecursor containing in situ formed unsaturated carbon atoms.

Embodiment 8

The process of Embodiment 7, wherein the effective hydroprocessingconditions comprise effective hydrotreating conditions, includingtemperatures of about 200° C. to about 450° C., or about 315° C. toabout 425° C.; pressures of about 250 psig (1.8 MPag) to about 5000 psig(34.6 MPag) or about 300 psig (2.1 MPag) to about 3000 psig (20.8 MPag);liquid hourly space velocities (LHSV) of about 0.1 hr⁻¹ to about 10hr⁻¹; and hydrogen treat rates of about 200 scf/B (35.6 m³/m³) to about10,000 scf/B (1781 m³/m³), or about 500 (89 m³/m³) to about 10,000 scf/B(1781 m³/m³); or wherein the effective hydroprocessing conditionscomprise second effective hydrocracking conditions, includingtemperatures of about 550° F. (288° C.) to about 840° F. (449° C.),hydrogen partial pressures of from about 250 psig to about 5000 psig(1.8 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05 h⁻¹to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to 1781 m³/m³(200 SCF/B to 10,000 SCF/B); or a combination thereof.

Embodiment 9

The process of any of Embodiments 7 or 8, further comprising exposingthe feedstock to a hydrotreating catalyst different from the mixed metalcatalyst under second effective hydrotreating conditions, the feedstockbeing exposed to the hydrotreating catalyst prior to the mixed metalcatalyst, after the mixed metal catalyst but prior to the separating ofthe hydroprocessed effluent, or a combination thereof, the secondeffective hydrotreating conditions including temperatures of about 200°C. to about 450° C., or about 315° C. to about 425° C.; pressures ofabout 250 psig (1.8 MPag) to about 5000 psig (34.6 MPag) or about 300psig (2.1 MPag) to about 3000 psig (20.8 MPag); liquid hourly spacevelocities (LHSV) of about 0.1 hr⁻¹ to about 10 hr⁻¹; and hydrogen treatrates of about 200 scf/B (35.6 m³/m³) to about 10,000 scf/B (1781m³/m³), or about 500 (89 m³/m³) to about 10,000 scf/B (1781 m³/m³).

Embodiment 10

The process of any of Embodiments 7 to 9, further comprising exposingthe feedstock to a hydrocracking catalyst different from the mixed metalcatalyst under third effective hydrocracking conditions, the feedstockbeing exposed to the hydrocracking catalyst prior to the mixed metalcatalyst, after the mixed metal catalyst but prior to the separating ofthe hydroprocessed effluent, or a combination thereof, the thirdeffective hydrocracking conditions including temperatures of about 550°F. (288° C.) to about 840° F. (449° C.), hydrogen partial pressures offrom about 250 psig to about 5000 psig (1.8 MPag to 34.6 MPag), liquidhourly space velocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogen treatgas rates of from 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to 10,000 SCF/B).

Embodiment 11

The process of any of Embodiments 7 to 10, wherein separating thehydroprocessed effluent to form at least a gas phase effluent and aliquid hydroprocessed effluent comprises separating the hydroprocessedeffluent to form a hydroprocessed distillate fuel fraction and a higherboiling hydrotreated fraction, the hydroprocessed distillate fuelfraction having a T95 boiling point of about 750° F. or less.

Embodiment 12

The process of any of Embodiments 7 to 11, wherein the effectivehydrocracking conditions include temperatures of about 550° F. (288° C.)to about 840° F. (449° C.), hydrogen partial pressures of from about 250psig to about 5000 psig (1.8 MPag to 34.6 MPag), liquid hourly spacevelocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates offrom 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to 10,000 SCF/B).

Embodiment 13

The process of any of Embodiments 7 to 12, wherein the effectivecatalytic dewaxing conditions including temperatures of about 200° C. toabout 450° C., preferably about 270° C. to about 400° C., hydrogenpartial pressures of about 1.8 MPag to about 34.6 MPag (250 psig to 5000psig), preferably about 4.8 MPag to about 20.8 MPag, liquid hourly spacevelocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates ofabout 35.6 m³/m³ (200 SCF/B) to about 1781 m³/m³ (10,000 scf/B),preferably about 178 m³/m³ (1000 SCF/B) to about 890.6 m³/m³ (5000SCF/B).

Embodiment 14

The process of any of Embodiments 7 to 13, the process furthercomprising exposing at least a portion of the optionally hydrocrackedeffluent to a hydrofinishing catalyst under effective hydrofinishingconditions, the effective hydrofinishing conditions includingtemperatures from about 125° C. to about 425° C., preferably about 180°C. to about 280° C., total pressures from about 500 psig (3.4 MPa) toabout 3000 psig (20.7 MPa), preferably about 1500 psig (10.3 MPa) toabout 2500 psig (17.2 MPa), liquid hourly space velocities from about0.1 hr⁻¹ to about 5 hr⁻¹ LHSV, preferably about 0.5 hr⁻¹ to about 1.5hr⁻¹, and hydrogen treat gas rates of from 500 to 5000 scf/B (89 to 890m³/m³), the at least a portion of the optionally hydrocracked effluentbeing exposed to the hydrofinishing catalyst prior to the dewaxingcatalyst, after the dewaxing catalyst, or a combination thereof.

Embodiment 15

The process of any of Embodiments 7 to 14, the process furthercomprising exposing at least a portion of the optionally hydrocrackedeffluent to an aromatic saturation catalyst under effective aromaticsaturation conditions, the effective aromatic saturation conditionsincluding temperatures from about 200° C. to about 425° C., preferablyabout 225° C. to about 325° C., total pressures from about 500 psig (3.4MPa) to about 3000 psig (20.7 MPa), preferably about 1500 psig (10.3MPa) to about 2500 psig (17.2 MPa), liquid hourly space velocities fromabout 0.1 hr⁻¹ to about 5 hr⁻¹ LHSV, preferably about 0.5 hr⁻¹ to about1.5 hr⁻¹, and hydrogen treat gas rates of from 500 to 5000 scf/B (89 to890 m³/m³), the at least a portion of the optionally hydrocrackedeffluent being exposed to the aromatic saturation catalyst prior to thedewaxing catalyst, after the dewaxing catalyst, or a combinationthereof.

Embodiment 16

The process of any of Embodiments 7 to 15, further comprising separatingthe optionally hydrocracked, dewaxed effluent to form at least alubricant boiling range fraction and a distillate boiling rangefraction.

Embodiment 17

The process of any of the above embodiments, wherein the catalystprecursor composition is treated first with said first organic compoundand second with said second organic compound, or wherein the catalystprecursor composition is treated first with said second organic compoundand second with said first organic compound, or wherein the catalystprecursor composition is treated simultaneously with said first organiccompound and with said second organic compound.

Embodiment 18

The process of any of the above embodiments, wherein said at least onemetal from Group 6 is Mo, W, or a combination thereof, and wherein saidat least one metal from Groups 8-10 is Co, Ni, or a combination thereof.

Embodiment 19

The process of any of the above embodiments, wherein the mixed metalcatalyst precursor composition is a bulk metal hydroprocessing catalystprecursor composition consisting essentially of the reaction product, anoxide form of the at least one metal from Group 6, an oxide form of theat least one metal from Groups 8-10, and optionally about 20 wt % orless of a binder.

EXAMPLES Example Hydrodentirogenation Activity

Table 1 below shows results from processing a vacuum gas oil feedstockin the presence of various catalysts in order to determine a relativeactivity for hydrodenitrogenation. For the processing runs shown inTable 1, a vacuum gas oil feed was exposed to a comparative bulkcatalyst and a catalyst formed from a suitable precursor as describedherein. The commercially available comparative bulk catalyst correspondsto a NiMoW bulk catalyst prepared according to the methods in U.S. Pat.Nos. 6,620,313; 7,232,515; or 7,513,989. Catalyst A corresponds to a NiWcatalyst made from a suitable precursor as described above.

As shown in Table 1, the reaction conditions used for processing thevacuum gas oil feed in the presence of each catalysts were the same.However, based on the superior hydrodenitrogenation activity of CatalystA, processing the feed in the presence of Catalyst A produced ahydrodenitrogenated effluent (total liquid product) with a significantlylower nitrogen content relative to processing the feed in the presenceof the comparative bulk catalyst.

TABLE 1 Hydrodenitrogenation Activity Comparative VGO Bulk Feed CatalystCatalyst A Conditions LHSV hr−1 1.1 1.1 Temp ° C. 365 365 TGR scf/bbl5000 5000 H2 pressure psig 1200 1200 Total Liquid Product N wppm 1614380 110 Relative HDN volume % 100 180 activity

Example Improved Aromatic Saturation Activity During Lubricant BasestockProduction

FIG. 2 shows results from processing a feedstock in a process train forproduction of a lubricant basestock product. For the processing runs inFIG. 2, a heavy neutral feed produced by solvent processing wasprocessed under raffinate hydroconversion conditions in the presence ofone of three types of catalyst systems. One catalyst corresponded to thecommercially available comparative bulk catalyst described above. Asecond catalyst corresponded to Catalyst A. A third catalyst systemcorresponded to a 50/50 mixture by volume of the commercially availablecomparative bulk catalyst and a commercially available NiMo supportedhydrotreating catalyst. The third catalyst system has a similar activityfor hydrodesulfurization and hydrodenitrogenation compared to theactivity of Catalyst A.

After exposing the heavy neutral feed to a catalyst under raffinatehydroconversion conditions, the 700° F.+ fraction of the total liquidproduct was a) used in a catalytic dewaxing step to form a lubricantbasestock product and b) used in a solvent dewaxing step to form adewaxed oil product. These additional products were characterized asshown in FIG. 2.

As shown in FIG. 2, under similar processing conditions, the totalliquid product produced from raffinate hydroconversion in the presenceof Catalyst A had a substantially lower aromatics content and lower 3+ring aromatics content than the total liquid product generated using thecomparative bulk catalyst. Catalyst A also produced lower aromaticscontents and lower 3+ ring aromatics contents relative to the mixedcatalyst system which had similar hydrodesulfurization andhydrodenitrogenation activity. This demonstrates that Catalyst A canprovide an unexpected benefit of improved aromatic saturation whenprocessing a feed suitable for lubricant basestock production. As shownin FIG. 2, this additional benefit in aromatics saturation can beachieved while producing a substantially similar yield at constantproduct quality relative to other catalyst systems, such as the mixedcatalyst system.

Although the present disclosure has been described in terms of specificembodiments, it is not so limited. Suitable alterations/modificationsfor operation under specific conditions should be apparent to thoseskilled in the art. It is therefore intended that the following claimsbe interpreted as covering all such alterations/modifications as fallwithin the true spirit/scope of the disclosure.

What is claimed is:
 1. A process for selectively hydroconverting araffinate produced from solvent refining a lubricating oil feedstock,comprising: conducting the lubricating oil feedstock to a solventextraction zone and separating therefrom an aromatics rich extract and aparaffins rich raffinate; stripping the raffinate of solvent to producea raffinate feed having a dewaxed oil viscosity index from 80 to 105 anda final boiling point of no greater than 650° C.; passing the raffinatefeed to a first hydroconversion zone and processing the raffinate feedin the presence of a mixed metal catalyst under hydroconversionconditions; and passing the first hydroconverted raffinate to a secondreaction zone and conducting cold hydrofinishing of the firsthydroconverted raffinate in the presence of a hydrofinishing catalystunder cold hydrofinishing conditions, wherein the mixed metal catalystcomprises a sulfided mixed metal catalyst formed by sulfiding a mixedmetal catalyst precursor composition, the mixed metal catalyst precursorcomposition being produced by a) heating a composition comprising atleast one metal from Group 6 of the Periodic Table of the Elements, atleast one metal from Groups 8-10 of the Periodic Table of the Elements,and a reaction product formed from (i) a first organic compoundcontaining at least one amine group, and (ii) a second organic compoundseparate from said first organic compound and containing at least onecarboxylic acid group to a temperature from 195° C. to 260° C. for atime sufficient for the first and second organic compounds to form areaction product in situ that contains an amide moiety, unsaturatedcarbon atoms not present in the first or second organic compounds, orboth; b) heating a composition comprising one metal from Group 6 of thePeriodic Table of the Elements, at least one metal from Groups 8-10 ofthe Periodic Table of the Elements, and a reaction product formed from(iii) a first organic compound containing at least one amine group andat least 10 carbon atoms or (iv) a second organic compound containing atleast one carboxylic acid group and at least 10 carbon atoms, but notboth (iii) and (iv), wherein the reaction product contains additionalunsaturated carbon atoms, relative to (iii) the first organic compoundor (iv) the second organic compound, wherein the metals of the catalystprecursor composition are arranged in a crystal lattice, and wherein thereaction product is not located within the crystal lattice, to atemperature from 195° C. to 260° C. for a time sufficient for the firstor second organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds; or c) heating a composition comprising at least onemetal from Group 6 of the Periodic Table of the Elements, at least onemetal from Groups 8-10 of the Periodic Table of the Elements, and apre-formed amide formed from (v) a first organic compound containing atleast one amine group, and (vi) a second organic compound separate fromsaid first organic compound and containing at least one carboxylic acidgroup, to form additional in situ unsaturated carbon atoms not presentin the first organic compound, the second organic compound, or both, butnot for so long that the pre-formed amide substantially decomposes,thereby forming a catalyst precursor containing in situ formedunsaturated carbon atoms.
 2. The process of claim 1, further comprisingpassing the raffinate feed into a second hydroconversion zone andprocessing the raffinate feed in the presence of a hydroconversioncatalyst under second effective hydroconversion conditions, theraffinate feed being passed into the second hydroconversion zone priorto being passed into the first hydroconversion zone or after beingpassed into the first hydroconversion zone.
 3. The process of claim 1,wherein the hydroconversion conditions in the first hydroconversionzone, the second hydroconversion zone, or both the first and secondhydroconversion zones include temperatures of from 250° C. to 420° C.,hydrogen pressures of from 300 to 3000 psig (2170 to 20786 kPa), liquidhourly space velocities of from 0.1 to 10 hr⁻¹, and hydrogen treat gasrates of from 500 to 5000 scf/B (89 to 890 m³/m³).
 4. The process ofclaim 1, wherein the cold hydrofinishing conditions include temperaturesof from 150° C. to 360° C., hydrogen pressures of from 300 to 3000 psig(2170 to 20786 kPa), liquid hourly space velocities of from 0.1 to 10and hydrogen treat gas rates of from 500 to 5000 scf/B (89 to 890m³/m³).
 5. The process of claim 1, wherein solvent in the solventextraction zone is at least one of furfural, phenol orN-methyl-2-pyrrolidone.
 6. The process of claim 1, wherein the coldhydrofinishing step is preceded by or followed by dewaxing, the dewaxingcomprising solvent dewaxing under solvent dewaxing conditions, catalyticdewaxing under catalytic dewaxing conditions, or a combination thereof.7. The process of claim 1, wherein the catalyst precursor composition istreated first with said first organic compound and second with saidsecond organic compound, or wherein the catalyst precursor compositionis treated first with said second organic compound and second with saidfirst organic compound, or wherein the catalyst precursor composition istreated simultaneously with said first organic compound and with saidsecond organic compound.
 8. The process of claim 1, wherein said atleast one metal from Group 6 is Mo, W, or a combination thereof, andwherein said at least one metal from Groups 8-10 is Co, Ni, or acombination thereof.
 9. The process of claim 1, wherein the mixed metalcatalyst precursor composition is a bulk metal hydroprocessing catalystprecursor composition consisting essentially of the reaction product, anoxide form of the at least one metal from Group 6, an oxide form of theat least one metal from Groups 8-10, and optionally 20 wt % or less of abinder.
 10. A process for producing a lubricating oil feedstock,comprising: exposing a feedstock to a mixed metal catalyst undereffective hydroprocessing conditions to form a hydroprocessed effluent;separating the hydroprocessed effluent to form at least a gas phaseeffluent and a liquid hydroprocessed effluent; optionally exposing atleast a portion of the liquid hydroprocessed effluent to a hydrocrackingcatalyst under effective hydrocracking conditions to form a hydrocrackedeffluent; exposing at least a portion of the optionally hydrocrackedeffluent to a dewaxing catalyst under effective catalytic dewaxingconditions to form a hydrocracked, dewaxed effluent, wherein the mixedmetal catalyst comprises a sulfided mixed metal catalyst formed bysulfiding a mixed metal catalyst precursor composition, the mixed metalcatalyst precursor composition being produced by a) heating acomposition comprising at least one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a reaction product formed from (i) afirst organic compound containing at least one amine group, and (ii) asecond organic compound separate from said first organic compound andcontaining at least one carboxylic acid group to a temperature from 195°C. to 250° C. for a time sufficient for the first and second organiccompounds to form a reaction product in situ that contains an amidemoiety, unsaturated carbon atoms not present in the first or secondorganic compounds, or both; b) heating a composition comprising onemetal from Group 6 of the Periodic Table of the Elements, at least onemetal from Groups 8-10 of the Periodic Table of the Elements, and areaction product formed from (iii) a first organic compound containingat least one amine group and at least 10 carbon atoms or (iv) a secondorganic compound containing at least one carboxylic acid group and atleast 10 carbon atoms, but not both (iii) and (iv), wherein the reactionproduct contains additional unsaturated carbon atoms, relative to (iii)the first organic compound or (iv) the second organic compound, whereinthe metals of the catalyst precursor composition are arranged in acrystal lattice, and wherein the reaction product is not located withinthe crystal lattice, to a temperature from 195° C. to 250° C. for a timesufficient for the first or second organic compounds to form a reactionproduct in situ that contains unsaturated carbon atoms not present inthe first or second organic compounds; or c) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a pre-formed amide formed from (v) a first organiccompound containing at least one amine group, and (vi) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group, to form additional in situ unsaturatedcarbon atoms not present in the first organic compound, the secondorganic compound, or both, but not for so long that the pre-formed amidesubstantially decomposes, thereby forming a catalyst precursorcontaining in situ formed unsaturated carbon atoms.
 11. The process ofclaim 10, wherein the effective hydroprocessing conditions compriseeffective hydrotreating conditions, including temperatures of 200° C. to450° C.; pressures of 250 psig (1.8 MPag) to 5000 psig (34.6 MPag);liquid hourly space velocities (LHSV) of 0.1 hr⁻¹ to 10 hr⁻¹; andhydrogen treat rates of 200 scf/B (35.6 m³/m³) to 10,000 scf/B (1781m³/m³).
 12. The process of claim 10, wherein the effectivehydroprocessing conditions comprise second effective hydrocrackingconditions, including temperatures of 550° F. (288° C.) to 840° F. (449°C.), hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPagto 34.6 MPag), liquid hourly space velocities of from 0.05 h⁻¹ to 10h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to 1781 m³/m³ (200SCF/B to 10,000 SCF/B).
 13. The process of claim 10, further comprisingexposing the feedstock to a hydrotreating catalyst different from themixed metal catalyst under second effective hydrotreating conditions,the feedstock being exposed to the hydrotreating catalyst prior to themixed metal catalyst, after the mixed metal catalyst but prior to theseparating of the hydroprocessed effluent, or a combination thereof. 14.The process of claim 10, further comprising exposing the feedstock to ahydrocracking catalyst different from the mixed metal catalyst underthird effective hydrocracking conditions, the feedstock being exposed tothe hydrocracking catalyst prior to the mixed metal catalyst, after themixed metal catalyst but prior to the separating of the hydroprocessedeffluent, or a combination thereof.
 15. The process of claim 10, whereinseparating the hydroprocessed effluent to form at least a gas phaseeffluent and a liquid hydroprocessed effluent comprises separating thehydroprocessed effluent to form a hydroprocessed distillate fuelfraction and a higher boiling hydrotreated fraction, the hydroprocesseddistillate fuel fraction having a T95 boiling point of 750° F. or less.16. The process of claim 10, wherein the effective hydrocrackingconditions including temperatures of 550° F. (288° C.) to 840° F. (449°C.), hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPagto 34.6 MPag), liquid hourly space velocities of from 0.05 h⁻¹ to 10h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to 1781 m³/m³ (200SCF/B to 10,000 SCF/B).
 17. The process of claim 10, wherein theeffective catalytic dewaxing conditions including temperatures of 200°C. to 450° C., hydrogen partial pressures of 1.8 MPag to 34.6 MPag (250psig to 5000 psig), liquid hourly space velocities of from 0.05 h⁻¹ to10 h⁻¹, and hydrogen treat gas rates of 35.6 m³/m³ (200 SCF/B) to 1781m³/m³ (10,000 scf/B).
 18. The process of claim 10, the process furthercomprising exposing at least a portion of the optionally hydrocrackedeffluent to a hydrofinishing catalyst under effective hydrofinishingconditions, the effective hydrofinishing conditions includingtemperatures from 125° C. to 425° C., total pressures from 500 psig (3.4MPa) to 3000 psig (20.7 MPa), liquid hourly space velocities from 0.1hr⁻¹ to 5 hr⁻¹ LHSV, and hydrogen treat gas rates of from 500 to 5000scf/B (89 to 890 m³/m³), the at least a portion of the optionallyhydrocracked effluent being exposed to the hydrofinishing catalyst priorto the dewaxing catalyst, after the dewaxing catalyst, or a combinationthereof.
 19. The process of claim 10, the process further comprisingexposing at least a portion of the optionally hydrocracked effluent toan aromatic saturation catalyst under effective aromatic saturationconditions, the effective aromatic saturation conditions includingtemperatures from 200° C. to 425° C., total pressures from 500 psig (3.4MPa) to 3000 psig (20.7 MPa), liquid hourly space velocities from 0.1hr⁻¹ to 5 hr⁻¹ LHSV, and hydrogen treat gas rates of from 500 to 5000scf/B (89 to 890 m³/m³), the at least a portion of the optionallyhydrocracked effluent being exposed to the aromatic saturation catalystprior to the dewaxing catalyst, after the dewaxing catalyst, or acombination thereof.
 20. The process of claim 10, further comprisingseparating the optionally hydrocracked, dewaxed effluent to form atleast a lubricant boiling range fraction and a distillate boiling rangefraction.